CN104425815A - High-density spherical Ni-Co lithium aluminate material and preparation of precursor of the material - Google Patents
High-density spherical Ni-Co lithium aluminate material and preparation of precursor of the material Download PDFInfo
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- CN104425815A CN104425815A CN201310361978.6A CN201310361978A CN104425815A CN 104425815 A CN104425815 A CN 104425815A CN 201310361978 A CN201310361978 A CN 201310361978A CN 104425815 A CN104425815 A CN 104425815A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a method for preparing a Ni-Co-Al precursor material and a method for preparing a Ni-Co lithium aluminate material with the precursor material. The method for preparing the Ni-Co-Al precursor material comprises following steps: (1) preparing a solution A containing a nickel (II) salt and a cobalt (II) salt, a solution B containing an aluminum complex and an ammonia-containing inorganic strong alkali solution C, wherein the solution B is prepared by dissolving an inorganic aluminum salt and at least two complexing agents; (2) synchronously feeding the solution A and the solution B into a reactor with a flow speed controlled to enable a molar ratio of nickel ion, cobalt ion and aluminum ion to be (6-9):(0.5-2):(0.5-2) with addition of the solution C to maintain a pH value of the mixture system to be 10-12.7; and (3) after the solution A and the solution B are fed synchronously, performing solid-liquid separation and washing, drying and optionally sieving a separated solid product to obtain the Ni-Co-Al precursor material.
Description
Technical field
The present invention relates to field of lithium ion battery anode, particularly the preparation of a kind of high density spherical nickel-cobalt lithium aluminate material and presoma thereof.
Background technology
Current lithium ion battery has been widely used in various portable electrical equipment, as mobile phone, camera, notebook computer etc., along with carry-on electricity consumption of equipment amount constantly increases, to small volume, lighter in weight, specific capacity, the higher and good lithium rechargeable battery demand of security performance continues to increase the supporting manufacturer of each battery.LiNiO
2the positive electrode of doping Co element is provided with LiNiO simultaneously
2the specific discharge capacity that material is higher, stabilizes again the layer structure of material, enhances the cycle performance of material simultaneously, and representative materials can be expressed as LiNi
0.8co
0.2o
2, the positive electrode of this composition has compared to the good energy density of homologous series material.But this material also exist overcharging resisting ability, thermal stability poor, to discharge the more high defect of irreversible capacity first.For overcoming the above problems, make nickel cobalt material can be applied to commercialization field as early as possible, Chinese scholars has carried out a large amount of doping tests, to improve the chemical property of material.Wherein the doping of aluminium can the structure of stabilizing material, increases lithium ion diffusion coefficient, obviously suppresses the exothermic reaction of material, and therefore the cycle performance of material and overcharging resisting performance are improved significantly, and its representative composition can be expressed as LiNi
0.8co
0.15al
0.05o
2, i.e. NCA material.
NCA positive electrode belongs to mixes aluminium profiles Ni-Co series row positive electrode, and Chinese scholars has carried out the research reaching for more than ten years, but in view of restrictions such as its synthesis difficulty are comparatively large, technological requirement is complicated, has fettered the realization of its large-scale commercial application.NCA material is once once quiet, but the height ratio capacity performance of researchers to NCA material still cannot be forgotten, and the specific discharge capacity of 180mAh/g seems still attractive under the demand environment of high power performance.
At present, lithium ion battery material is the focus of current research in the application of dynamic field, and NCA positive electrode can possess larger market potential and application prospect with its high power capacity performance and higher-security and receive much concern in electrokinetic cell field.
But the preparation method of this material also exists larger problem always, be difficult to large-scale production.Because during trivalent aluminium ion precipitation, the solubility product constant of aluminium hydroxide is very little reach 1.3 × 10
-33, and the solubility product of nickel cobalt is all 10
-15the order of magnitude, therefore aluminum ions settling velocity is quickly, easily forms flocculent deposit and is difficult to filter, and is also difficult to form spherical macro precipitation.And mix lithium with this presoma and calcine the nickel cobalt lithium aluminate obtained, loose particles, structural stability is poor, and discharge capacity is on the low side.
The preparation method of current nickel cobalt aluminum mainly contains synthesis in solid state and liquid phase synthesis.Solid phase synthesis is generally to sinter after the compound of nickel, cobalt and aluminium and Li source compound mixing, but this solids mix mode can not reach the even of atomic level, and performance is difficult to give full play to; Although liquid phase method can head it off, complex process, poor-performing, to yield poorly.As: Chinese patent application 200810052730.0 discloses the preparation method of a kind spherical nickel-cobalt aluminum; Chinese patent application 201110140341.5 discloses a kind of first use Liquid preparation methods nickel cobalt precursor, on presoma, metallized aluminum is made nickel cobalt aluminium presoma, synthesized the method for nickel cobalt aluminum with the roasting of lithium source afterwards again; Chinese patent application 201010594744.2 discloses and a kind of in nickel cobalt aluminum solutions coprecipitation process, add oxidant make nickel cobalt aluminium oxidation of precursor be hydroxy cobalt nickel oxide aluminum, then carries out the nickel cobalt aluminum Preparation Method of mixed lithium roasting.ACS Appl.Mater.Interfaces2012,4,586-589 describes a kind of organic complex that aluminium butoxide and acetylacetone,2,4-pentanedione is mixed to form and is dissolved in ethanol and carries out coprecipitation reaction generating nickel cobalt aluminium presoma with nickel cobalt salt solution and aqueous slkali again, afterwards with the method for lithium source baking mixed formation nickel cobalt aluminum.
Nickel cobalt aluminum preparation method disclosed in patent application 200810052730.0 is that nickel cobalt aluminum salt solution is direct and aqueous slkali carries out coprecipitation reaction, although the fairly simple applicable suitability for industrialized production of this method, but comparatively fast easily form colloid because trivalent aluminium precipitates in coprecipitation process, make the nickel cobalt aluminium presoma crystallization of generation incomplete, pattern is irregular, and tap density is on the low side and electrical property is poor; Although method disclosed in patent application 201110140341.5 can prepare the higher nickel cobalt aluminium presoma of the better tap density of pattern and material, but aluminium element is coated on nickel cobalt precursor surface in the material that the method is prepared, part aluminium can not enter lattice in roasting process, nickel, cobalt, aluminium ion can not form atom level mixing, have impact on the performance of material; All ions all can be oxidized and form trivalent spherical hydroxy nickel oxide cobalt aluminium presoma by method disclosed in patent application 201010594744.2 in precursor power process, make presoma pattern rule tap density higher, but strong oxidizer can make a large amount of foreign ions enter lattice in liquid phase, the impurity of material is rolled up, and this kind of impurity cannot wash removing, this is unacceptable in commercial applications.ACS Appl.Mater.Interfaces2012,4, the nickel cobalt aluminum Preparation Method that 586-589 proposes can improve the degree of crystallinity of persursor material, be conducive to the raising of material physical and chemical performance, but the method preparation technology more complicated, excessive use organic solvent subsequent treatment difficulty strengthens, and the organo-aluminium source expensive raw material price used, the needs of large-scale production can not be adapted to.
Summary of the invention
For above-mentioned problems of the prior art, the present invention aim to provide a kind of can low cost, simple prepare the mixing of nickel cobalt aluminium element atom level, the high density spherical nickel-cobalt aluminum of better crystallinity degree and the method for presoma thereof.
Above-mentioned purpose of the present invention can be achieved through the following technical solutions.
1. prepare a method for nickel cobalt aluminium persursor material, described nickel cobalt aluminium persursor material can be used for preparing nickel cobalt lithium aluminate material, and described method comprises:
Step (1): preparation contains the solution A of nickel (II) salt and cobalt (II) salt; The solution B of aluminum-containing complex compound; With the inorganic strong alkali solution C containing ammonia, wherein aluminium complex solution B is by being dissolved in water preparing inorganic aluminate, at least two class complexing agents, described at least two class complexing agents are selected from first kind complexing agent, Equations of The Second Kind complexing agent and the 3rd class complexing agent, wherein said first kind complexing agent is alcamines complexing agent and ammoniacal liquor, described Equations of The Second Kind complexing agent is amino carboxylic acid salt complexing agent, and described 3rd class complexing agent is hydroxycarboxylic acid salt complexing agent
Step (2): by the solution A for preparing and solution B with in the flow velocity simultaneous implantation reactor controlled, nickel cobalt aluminium ion mol ratio is reached (6-9): (0.5-2): (0.5-2), add solution C simultaneously, so that the pH value of mixed system is remained between 10-12.7
Step (3): carry out Separation of Solid and Liquid after solution A and B are injected simultaneously, the solid product after separation through washing, dry and optional sieve after, obtain nickel cobalt aluminium persursor material.
2. the method according to the 1st, wherein said nickel (II) salt, cobalt (II) salt and aluminium salt are water-soluble inorganic salt independently of one another.
3. the method according to above-mentioned any one, wherein said nickel (II) salt, cobalt (II) salt and aluminium salt are selected from nickelous sulfate, nickel nitrate, nickel chloride, nickel acetate independently of one another; Cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt acetate; Aluminum nitrate, aluminum sulfate, aluminium chloride.
4. the method according to above-mentioned any one, in wherein said solution A, nickel cobalt ions mol ratio is 8: 1 to 4: 1.
5. the method according to above-mentioned any one, wherein said alcamines complexing agent comprises triethanolamine, diethanol amine; Described amino carboxylic acid salt complexing agent comprises EGTA, EDTA and EDETATE SODIUM; And described hydroxycarboxylic acid salt complexing agent comprises citric acid, tartaric acid, sulfosalicylic acid, gluconic acid sodium salt and salicylic acid.
6. the method according to above-mentioned any one, wherein in the preparation of solution B, controls the ratio of at least two class complexing agents mixed with inorganic aluminate, makes formed complex compound can be water-soluble.
7. the method according to above-mentioned any one, wherein in the preparation of solution B, controls solution ph between 2-5.
8. the method according to above-mentioned any one, wherein in the preparation of solution B, carries out the heating stir process under 30-80 degree Celsius.
9. the method according to above-mentioned any one, the strong base concentrations in wherein said strong base solution C is 2-10M.
10. the method according to above-mentioned any one, the ammonia content in wherein said strong base solution C is 2-6M.
11. methods according to above-mentioned any one, wherein in described step (2), before injection solution A and solution B, are equipped with end liquid in described reactor in advance.
12. methods according to above-mentioned any one, liquid of the wherein said end is water, or the mixture of water and ammoniacal liquor, or the mother liquor injecting last time, stay after reaction.
13. 1 kinds of methods preparing nickel cobalt lithium aluminate material, described method comprises:
The persursor material prepare the method according to above-mentioned any one and lithium source are according to Li: M=(1.1-1): 1 mixed in molar ratio, and wherein M represents the summation of nickel (II), cobalt (II) and aluminium; Then under the condition of logical oxygen, roasting is carried out; After cooling, fragmentation is sieved.
14. methods according to the 13rd, wherein said roasting is two-stage method roasting, wherein first paragraph temperature 300-650 degree, roasting 2-10h, second segment temperature 670-820 degree, roasting 12-24h.
15. methods according to any one of 13-14, wherein said mixing comprises wet-mixed, dry mixed and three-dimensional blender.
16. methods according to any one of 13-15, wherein said nickel cobalt lithium aluminate material is the positive electrode for lithium ion battery.
By method of the present invention, can produce the high density spherical nickel-cobalt aluminum of the mixing of nickel cobalt aluminium element atom level, better crystallinity degree under the prerequisite not rolling up cost, its charge/discharge capacity and first efficiency improve.And method of the present invention is simple, large-scale industrial production can be carried out.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the nickel cobalt lithium aluminate material according to the embodiment of the present invention 1.
Fig. 2 is the SEM photo of precursor material (left side) according to the embodiment of the present invention 1 and nickel cobalt lithium aluminate material (right side).
Fig. 3 is the charging and discharging curve figure of the battery adopting the nickel cobalt lithium aluminate material of the embodiment of the present invention 1 to make.
Fig. 4 is the loop test curve of the battery adopting the nickel cobalt lithium aluminate material of the embodiment of the present invention 1 to make.
Embodiment
The present inventor forms Al (OH) for aluminium ion in aqueous phase
3settling velocity want obviously to be easy to be formed colloid or the problem of the blowball that grain reunites of being wadded a quilt with cotton by nanometer faster than nickel cobalt ions, consider by first Al ion and complexing agent being carried out complexing, then carry out co-precipitation to control its settling velocity with nickel and cobalt ions.But, there is respective shortcoming after finding Al ion and single complexing agent complexes in inventor, the complex dissolves degree formed as Al ion and triethanolamine is higher, but due to the complexing power of triethanolamine poor, the stable pH value range of complex compound is very narrow, and Al ion is easily hydrolyzed; After Al ion and EDTA complexing, although EDTA complexing power is comparatively strong, the complex dissolves degree formed is low, easily forms precipitation; Form complex compound after Al ion and sulfosalicylic acid complexing comparatively stable, but dispersibility is poor, easily reunites in course of reaction, affects product homogeneity.For this reason, inventor designs a kind of method adopting multiple complexing agent to form clad aluminum complex compound, wherein from first kind complexing agent (alcamines complexing agent and ammoniacal liquor), Equations of The Second Kind complexing agent (amino carboxylic acid salt complexing agent) and the 3rd class complexing agent (hydroxycarboxylic acid salt complexing agent), select at least two class complexing agents, as the complexing agent with aluminium complexing.By selecting the combination of the suitable above complexing agent of two classes, obtain the aluminium complex of water soluble, the slow hydrolysis of meeting in neutrality or alkaline environment in acid condition, and this aluminium complex is hydrolyzed generation Al (OH) under strong basicity environment
3settling velocity can be suitable with nickel cobalt ions coprecipitation reaction speed, thus each element in nickel cobalt aluminium presoma is uniformly dispersed, crystallization is more complete, close structure, tap density is higher, use this presoma and lithium source carry out baking mixed after charge/discharge capacity and first efficiency also obtain larger raising, the complexing agent simultaneously owing to using is general industrial products, cheap, very low on product cost impact.
Although be reluctant to arrest in any theory, it is believed that by by appropriate aluminium source (such as aluminum nitrate etc.), at least two class complexing agents in suitable condition, such as pH between 2 ~ 5 and heat stir condition under, when mixing in water, Al
3+hydroxyl in ion and complexing agent and carboxyl generation complex reaction, with Al
3+for node defines a kind of network structure, this kind of network structure belongs to dissolubility hydrate, slowly can be hydrolyzed, form Al (OH) in neutrality or alkaline environment
3precipitation.The network character of multiple complexing agent like this and the complexing product of aluminium makes it possible to achieve desirable nickel cobalt aluminium presoma coprecipitation reaction, namely, when by appropriate aluminium ion complex solution and nickel and cobalt solution and stream adds in reactor, add simultaneously as precipitation reagent with the addition of the sodium hydroxide solution of ammoniacal liquor time, aluminium ion complex compound be hydrolyzed under strong basicity environment generate Al (OH)
3settling velocity can be suitable with nickel cobalt ions coprecipitation reaction speed, and its reaction speed is than direct Al
3+and OH
-reaction speed is slow, so just makes nickel cobalt ions and aluminum ions settling velocity substantially be consistent, thus can obtain the High-density spherical nickel-cobalt-aluminprecursor precursor material of the mixing of nickel cobalt aluminium element atom level, better crystallinity degree.
Be described below in detail of the present invention prepare nickel cobalt aluminium persursor material method and utilize this nickel cobalt aluminium persursor material to prepare the method for nickel cobalt lithium aluminate material.
The method preparing nickel cobalt aluminium persursor material of the present invention comprises: step (1) preparation contains the solution A of nickel (II) salt and cobalt (II) salt; The solution B of aluminum-containing complex compound; With the inorganic strong alkali solution C containing ammonia, wherein aluminium complex solution B is by being dissolved in water preparing inorganic aluminate, at least two class complexing agents; Step (2) by the solution A for preparing and solution B with in the flow velocity simultaneous implantation reactor controlled, nickel cobalt aluminium ion mol ratio is made to reach nickel cobalt aluminium ion mol ratio in nickel cobalt lithium aluminate material, add solution C, to remain between 10-12.7 by the pH value of mixed system simultaneously; After solution A and B are injected simultaneously, carry out Separation of Solid and Liquid with step (3), the solid product after separation through washing, dry and optional sieve after, obtain nickel cobalt aluminium persursor material.
The preparation of step (1) solution A, solution B and solution C:
Can be water-soluble inorganic salt independently of one another with nickel of the present invention (II) salt, cobalt (II) salt.As the representative example of water-soluble nickel (II) salt, nickelous sulfate can be enumerated, nickel nitrate, nickel chloride, nickel acetate etc.As the representative example of aqueous cobalt (II) salt, cobaltous sulfate can be enumerated, cobalt nitrate, cobalt chloride, cobalt acetate etc.
A certain amount of water soluble nickel salt and cobalt salt can be dissolved in preparation in deionized water and contain the solution A of nickel (II) salt and cobalt (II) salt, in solution A, the concentration of nickel cobalt salt can be generally 1.5M-2.5M, and nickel cobalt ions mol ratio can be Ni: Co=8: 1-4: 1.
As the compound method of the solution B of aluminum-containing complex compound, inorganic aluminate, at least two class complexing agents can be dissolved in water and prepare relative to Al (III) little over the ratio of amount with complexing agent.
At least two class complexing agents used in the present invention are selected from: the first kind complexing agent be made up of alcamines complexing agent and ammoniacal liquor, the Equations of The Second Kind complexing agent be made up of amino carboxylic acid salt complexing agent and the 3rd class complexing agent be made up of hydroxycarboxylic acid salt complexing agent.Alcamines complexing agent used in the present invention comprises triethanolamine, diethanol amine etc.; Amino carboxylic acid salt complexing agent comprises EGTA, EDTA and EDETATE SODIUM etc.; Hydroxycarboxylic acid salt complexing agent comprises citric acid, tartaric acid, sulfosalicylic acid, gluconic acid sodium salt, salicylic acid etc.In the preparation of solution B, control the ratio of at least two class complexing agents mixed with inorganic aluminate, make formed complex compound can be water-soluble.
Aluminium salt for aluminium complex solution B is inorganic aluminate, and preferred water miscible inorganic aluminate, the example includes but not limited to aluminum nitrate, aluminum sulfate, aluminium chloride etc.The concentration of aluminium ion in solution B can within the scope of 0.1M-1M.
In order to the aluminium complex obtaining water soluble in acid condition of the present invention, can slowly be hydrolyzed in neutrality or alkaline environment, in the process for preparation of solution B, control between 2-5 by the pH of solution, too high and too low pH value is unfavorable for the formation of stable aluminium complex.The control of pH can realize by adding inorganic acid such as sulfuric acid.Meanwhile, in order to promote the formation of aluminium complex, aluminium complex solution B can be prepared under condition of heating and stirring.Heating can be undertaken by water-bath etc., makes solution temperature reach 30-80 degree Celsius.Heating mixing time can be such as 1-2h.
In the present invention, the inorganic strong alkali solution C containing ammonia is used for realizing nickel cobalt aluminium presoma coprecipitation reaction as precipitation reagent.Inorganic strong alkali herein comprises NaOH, potassium hydroxide etc., and its concentration is 2-10M, preferred 5-10M.Ammonia containing 2-6M in inorganic strong alkali solution C, object controls settling velocity.Ammonia content is preferably 3-6M.
Step (2) nickel cobalt aluminium coprecipitation process
In the present invention, by the solution A that will prepare and solution B with in the flow velocity simultaneous implantation reactor controlled, nickel cobalt aluminium ion mol ratio is made to reach nickel cobalt aluminium ion mol ratio in nickel cobalt lithium aluminate material, add solution C simultaneously, the pH value of mixed system is remained between 10-12.7, between preferred 11-12.7, to realize the co-precipitation of nickel cobalt aluminium.
In order to realize the synchronous co-precipitation of nickel cobalt aluminium, the solution A prepared and solution B are selected suitable liquor capacity according to its respective concentration, and control injection rate, make solution A and solution B start inject and inject complete simultaneously, and the nickel cobalt aluminium ion mol ratio in reactor can reach such as (6-9) according to the nickel cobalt aluminium ion mol ratio in the nickel cobalt lithium aluminate material of expection: (0.5-2): (0.5-2) simultaneously.
Before injection solution A and solution B, in the reactor liquid of a certain amount of end is housed in advance, can be uniformly mixed in time the new solution injected.End liquid herein can be water, or the mixture of water and ammoniacal liquor, or injected last time, the mother liquor that stays after reaction.In addition, end liquid suitably can be heated, such as, be heated to 30-80 degree Celsius.
Step (3) reprocessing
Inject in solution A and B and after having reacted, carry out following reprocessing: by product Separation of Solid and Liquid; By the solid product washing after being separated, dry and optionally sieve, nickel cobalt aluminium persursor material can be obtained.
The washing of solid product can be carried out according to method well known in the art, such as, uses distilled water washing 3-5 time.Drying can the temperature at such as 100-150 degree Celsius in the dry instrument such as baking oven of routine be carried out.Dried solid generally can use the sieved sieve of 200-500 object.
The method preparing nickel cobalt lithium aluminate material of the present invention comprises: will according to persursor material of the present invention and lithium source according to Li: M=(1.1-1): the mixed in molar ratio of 1, and wherein M represents the summation of nickel (II), cobalt (II) and aluminium; Then under the condition of logical oxygen, roasting is carried out; After cooling, fragmentation is sieved, and obtains nickel cobalt lithium aluminate material.
Lithium source used in the present invention comprises various lithium salts, includes but not limited to lithium carbonate, lithium hydroxide, lithium acetate etc.
Persursor material of the present invention can carry out in several ways with mixing of lithium source, and persursor material solid wherein directly mixes with lithium source solid by such as dry mixed; Wet-mixed, wherein by persursor material and lithium source under the existence of liquid medium such as ethanol, use ball mill etc. to grind; And use the three-dimensional blender etc. of three-dimensional material mixer.
After persursor material mixes with lithium source, by mixture roasting under aerobic conditions.Roasting can be carried out in many ways, wherein preferred two-stage method roasting, that is, first paragraph temperature 300-650 degree, roasting 2-10h, second segment temperature 670-820 degree, roasting 12-24h.
After room temperature is down to by material after roasting, nickel cobalt lithium aluminate material of the present invention can be obtained after fragmentation is sieved.Such nickel cobalt lithium aluminate material may be used for the positive electrode of lithium ion battery.
Method of the present invention is used to prepare nickel cobalt lithium aluminate synthesis process simple, lower to equipment requirement, be applicable to suitability for industrialized production.And the nickel cobalt lithium aluminate material crystalline degree prepared is good, is spherical morphology, first charge-discharge capacity and efficiency high.
embodiment
Below, describe the present invention in more detail by embodiment, but these embodiments are only exemplary, and should not be construed as limitation of the scope of the invention.
Embodiment 1
By 1700g NiSO
46H
2o and 330g CoSO
47H
2o is dissolved in 4L deionized water and forms solution A, by 150g Al (NO
3)
39H
2o and 57g triethanolamine, the anhydrous sulfosalicylic acid of 150gEDTA, 42g are dissolved in 2L deionized water, after adding sulfuric acid adjustment pH=3, solution are placed in 75 degree of heating water bath blenders and stir 2h, form aluminium complex solution B; Preparation 4L concentration is the sodium hydroxide solution of 6M, adds after the ammoniacal liquor mixing of 1.2L concentration 28% as aqueous slkali C.2L mother liquor is added by 15L reactor, after being heated to 50 DEG C, and stream adds solution A and B, wherein solution A flow control is at 0.2L/h, the flow control of solution B is at 0.1L/h, open aqueous slkali C simultaneously, regulate aqueous slkali flow control reactor system pH between 12.0-12.5, adding of aqueous slkali is stopped after solution A and solution B all add reactor, after using deionized water to wash 3-5 time after Separation of Solid and Liquid, material is dried 12h in 120 DEG C of baking ovens, after crossing 200 mesh sieves, nickel cobalt aluminium persursor material can be obtained.By lithium carbonate and persursor material with Li: M=1.05: 1 ratio mix, in baking furnace under oxygen atmosphere at 300 DEG C roasting 4h, roasting 24h at 750 DEG C, the material fragmentation after roasting obtains LiNi after crossing 200 mesh sieves
0.8co
0.15al
0.05o
2material.
Through XRD test result as shown in Figure 1, material crystal structure is complete for this material, does not find assorted peak.Nickel cobalt aluminum (right side) from the SEM photo of Fig. 2 after visible persursor material (left side) and roasting is spherical morphology.LiNi
0.8co
0.15al
0.05o
2material particle mean size 8.2um, tap density 2.35g/cm
3.To make after 2032 button cells first charge-discharge curve under 0.1C current density 3.0-4.3V voltage at normal temperatures as shown in Figure 3, wherein charging capacity is 214.4mAh/g, and discharge capacity is 195.5mAh/g, and efficiency is 91.2% first.As shown in Figure 4, wherein 50 circulation conservation rates are 85.5% for the loop test curve of this battery under 1C current density 3.0-4.3V voltage.
Embodiment 2:
By 1700g NiSO
46H
2o and 220g CoSO
47H
2o is dissolved in 4L deionized water and forms solution A, by 300g Al (NO
3)
39H
2o and 105g diethanol amine, 115g tartaric acid are dissolved in 2L deionized water, after adding sulfuric acid adjustment pH=2, solution are placed in 50 degree of heating water bath blenders and stir 2h, form aluminium complex solution B; Preparation 4L concentration is the sodium hydroxide solution of 10M, adds after the ammoniacal liquor mixing of 3L concentration 28% as aqueous slkali C.2L mother liquor is added by 15L reactor, after being heated to 50 DEG C, by the flow control of solution A and B together with 0.2L/h and stream adds solution A and B, open aqueous slkali C regulates aqueous slkali flow control reactor system pH between 11.5-12.0 simultaneously, adding of aqueous slkali is stopped after solution A and solution B all add reactor, after using deionized water to wash 3-5 time after Separation of Solid and Liquid, material is dried 8h in 150 DEG C of baking ovens, after crossing 200 mesh sieves, nickel cobalt aluminium persursor material can be obtained.By lithium carbonate and persursor material with Li: M=1.05: 1 ratio mix, in baking furnace under oxygen atmosphere at 300 DEG C roasting 4h, roasting 24h at 750 DEG C, the material fragmentation after roasting obtains LiNi after crossing 200 mesh sieves
0.8co
0.1al
0.1o
2material.
The LiNi obtained
0.8co
0.1al
0.1o
2material particle mean size 7.9um, tap density 2.3g/cm
3.According to the method identical with embodiment 1 this material made 2032 button cells and measure first charge-discharge curve and loop test curve, the initial charge capacity of this battery at normal temperatures under 0.1C current density 3.0-4.3V voltage is 208.4mAh/g, discharge capacity is 189mAh/g, and efficiency is 90.7% first.Lower 50 the circulation conservation rates of 1C current density 3.0-4.3V voltage are 87.3%.
Embodiment 3
By 1487.5g NiSO
46H
2o and 440g CoSO
47H
2o is dissolved in 4L deionized water and forms solution A, by 300g Al (NO
3)
39H
2o and 102gEGTA, 83g tartaric acid, the anhydrous sulfosalicylic acid of 135g, 57g triethanolamine are dissolved in 2L deionized water, after adding sulfuric acid adjustment pH=2, solution are placed in 80 degree of heating water bath blenders and stir 2h, form aluminium complex solution B; Preparation 4L concentration is the sodium hydroxide solution of 10M, adds after the ammoniacal liquor mixing of 4L concentration 28% as aqueous slkali C.2L mother liquor is added by 15L reactor, after being heated to 50 DEG C, by the flow control of solution A and B together with 0.2L/h and stream adds solution A and B, open aqueous slkali regulates aqueous slkali C flow control reactor system pH between 12.5-12.7 simultaneously, adding of aqueous slkali is stopped after solution A and solution B all add reactor, after using deionized water to wash 3-5 time after Separation of Solid and Liquid, material is dried 12h in 120 DEG C of baking ovens, after crossing 200 mesh sieves, nickel cobalt aluminium persursor material can be obtained.By lithium carbonate and persursor material with Li: M=1.05: 1 ratio mix, in baking furnace under oxygen atmosphere at 600 DEG C roasting 4h, roasting 12h at 800 DEG C, the material fragmentation after roasting obtains LiNi after crossing 200 mesh sieves
0.7co
0.2al
0.1o
2material.
The LiNi obtained
0.7co
0.2al
0.1o
2material particle mean size 8.4um, tap density 2.36g/cm
3.According to the method identical with embodiment 1 this material made 2032 button cells and measure first charge-discharge curve and loop test curve, the initial charge capacity of this battery at normal temperatures under 0.1C current density 3.0-4.3V voltage is 203.5mAh/g, discharge capacity is 181.5mAh/g, and efficiency is 89.2% first.Lower 50 the circulation conservation rates of 1C current density 3.0-4.3V voltage are 89.1%.
Embodiment 4
By 1700g NiSO
46H
2o and 330g CoSO
47H
2o is dissolved in 4L deionized water and forms solution A, by 150g Al (NO
3)
39H
2o and 150gEDTA, 120ml ammoniacal liquor are dissolved in 2L deionized water, after adding sulfuric acid adjustment pH=4.5, solution are placed in 75 degree of heating water bath blenders and stir 2h, form aluminium complex solution B; Preparation 4L concentration is the sodium hydroxide solution of 6M, adds after the ammoniacal liquor mixing of 2L concentration 28% as aqueous slkali C.2L mother liquor is added by 15L reactor, after being heated to 50 DEG C, and stream adds solution A and B, wherein solution A flow control is at 0.2L/h, the flow control of solution B is at 0.1L/h, open aqueous slkali simultaneously, regulate aqueous slkali C flow control reactor system pH between 11.9-12.2, adding of aqueous slkali is stopped after solution A and solution B all add reactor, after using deionized water to wash 3-5 time after Separation of Solid and Liquid, material is dried 12h in 120 DEG C of baking ovens, after crossing 200 mesh sieves, nickel cobalt aluminium persursor material can be obtained.By lithium carbonate and persursor material with Li: M=1.07: 1 ratio mix, in baking furnace under oxygen atmosphere at 400 DEG C roasting 4h, roasting 20h at 750 DEG C, the material fragmentation after roasting obtains LiNi after crossing 200 mesh sieves
0.8co
0.15al
0.05o
2material.
The LiNi obtained
0.8co
0.15al
0.05o
2material particle mean size 6.9um, tap density 2.2g/cm
3.According to the method identical with embodiment 1 this material made 2032 button cells and measure first charge-discharge curve and loop test curve, the initial charge capacity of this battery at normal temperatures under 0.1C current density 3.0-4.3V voltage is 213.5mAh/g, discharge capacity is 192.5mAh/g, and efficiency is 90.2% first.Lower 50 the circulation conservation rates of 1C current density 3.0-4.3V voltage are 84.9%.
Embodiment 5
By 1487.5g NiSO
46H
2o and 440g CoSO
47H
2o is dissolved in 4L deionized water and forms solution A, by 600g Al (NO
3)
39H
2the anhydrous sulfosalicylic acid of O and 105gEDTA, 214g is dissolved in 4L deionized water, after adding sulfuric acid adjustment pH=3, solution is placed in 30 degree of heating water bath blenders and stirs 2h, form aluminium complex solution B; Preparation 4L concentration is the sodium hydroxide solution of 8M, adds after the ammoniacal liquor mixing of 4L concentration 28% as aqueous slkali C.2L mother liquor is added by 15L reactor, after being heated to 50 DEG C, by the flow control of solution A and B together with 0.15L/h and stream adds solution A and B, open aqueous slkali regulates aqueous slkali C flow control reactor system pH between 11.2-11.5 simultaneously, adding of aqueous slkali is stopped after solution A and solution B all add reactor, after using deionized water to wash 3-5 time after Separation of Solid and Liquid, material is dried 12h in 120 DEG C of baking ovens, after crossing 200 mesh sieves, nickel cobalt aluminium persursor material can be obtained.By lithium carbonate and persursor material with Li: M=1.05: 1 ratio mix, in baking furnace under oxygen atmosphere at 600 DEG C roasting 4h, roasting 16h at 800 DEG C, the material fragmentation after roasting obtains LiNi after crossing 200 mesh sieves
0.7co
0.1al
0.2o
2material.
The LiNi obtained
0.7co
0.1al
0.2o
2material particle mean size 8.4um, tap density 2.36g/cm
3.According to the method identical with embodiment 1 this material made 2032 button cells and measure first charge-discharge curve and loop test curve, the initial charge capacity of this battery at normal temperatures under 0.1C current density 3.0-4.3V voltage is 204.7mAh/g, discharge capacity is 174.8mAh/g, and efficiency is 85.4% first.Lower 50 the circulation conservation rates of 1C current density 3.0-4.3V voltage are 87.8%.
Claims (16)
1. prepare a method for nickel cobalt aluminium persursor material, described nickel cobalt aluminium persursor material can be used for preparing nickel cobalt lithium aluminate material, and described method comprises:
Step (1): preparation contains the solution A of nickel (II) salt and cobalt (II) salt; The solution B of aluminum-containing complex compound; With the inorganic strong alkali solution C containing ammonia, wherein solution B is by being dissolved in water preparing inorganic aluminate, at least two class complexing agents, described at least two class complexing agents are selected from first kind complexing agent, Equations of The Second Kind complexing agent and the 3rd class complexing agent, wherein said first kind complexing agent is alcamines complexing agent and ammoniacal liquor, described Equations of The Second Kind complexing agent is amino carboxylic acid salt complexing agent, and described 3rd class complexing agent is hydroxycarboxylic acid salt complexing agent
Step (2): by the solution A for preparing and solution B with in the flow velocity simultaneous implantation reactor controlled, nickel cobalt aluminium ion mol ratio is reached (6-9): (0.5-2): (0.5-2), add solution C simultaneously, so that the pH value of mixed system is remained between 10-12.7
Step (3): carry out Separation of Solid and Liquid after solution A and B are injected simultaneously, the solid product after separation through washing, dry and optional sieve after, obtain nickel cobalt aluminium persursor material.
2. method according to claim 1, wherein said nickel (II) salt, cobalt (II) salt and aluminium salt are water-soluble inorganic salt independently of one another.
3. method according to claim 1, wherein said nickel (II) salt, cobalt (II) salt and aluminium salt are selected from nickelous sulfate, nickel nitrate, nickel chloride, nickel acetate independently of one another; Cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt acetate; Aluminum nitrate, aluminum sulfate, aluminium chloride.
4. method according to claim 1, in wherein said solution A, nickel cobalt ions mol ratio is 8: 1 to 4: 1.
5. method according to claim 1, wherein said alcamines complexing agent comprises triethanolamine, diethanol amine; Described amino carboxylic acid salt complexing agent comprises EGTA, EDTA and EDETATE SODIUM; And described hydroxycarboxylic acid salt complexing agent comprises citric acid, tartaric acid, sulfosalicylic acid, gluconic acid sodium salt and salicylic acid.
6. method according to claim 1, wherein in the preparation of solution B, controls the ratio of at least two class complexing agents mixed with inorganic aluminate, makes formed complex compound can be water-soluble.
7. method according to claim 1, wherein in the preparation of solution B, controls solution ph between 2-5.
8. method according to claim 1, wherein in the preparation of solution B, carries out the heating stir process under 30-80 degree Celsius.
9. method according to claim 1, the strong base concentrations in wherein said strong base solution C is 2-10M.
10. method according to claim 1, the ammonia content in wherein said strong base solution C is 2-6M.
11. methods according to claim 1, wherein in described step (2), before injection solution A and solution B, are equipped with end liquid in described reactor in advance.
12. methods according to claim 11, liquid of the wherein said end is water, or the mixture of water and ammoniacal liquor, or injected last time, the mother liquor that stays after reaction.
13. 1 kinds of methods preparing nickel cobalt lithium aluminate material, described method comprises:
The persursor material prepare method according to claim 1 and lithium source are according to Li: M=(1.1-1): the mixed in molar ratio of 1, and wherein M represents the summation of nickel (II), cobalt (II) and aluminium; Then under the condition of logical oxygen, roasting is carried out; After cooling, fragmentation is sieved.
14. methods according to claim 13, wherein said roasting is two-stage method roasting, wherein first paragraph temperature 300-650 degree, roasting 2-10h, second segment temperature 670-820 degree, roasting 12-24h.
15. methods according to claim 13, wherein said mixing comprises wet-mixed, dry mixed and three-dimensional blender.
16. methods according to claim 13, wherein said nickel cobalt lithium aluminate material is the positive electrode for lithium ion battery.
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| CN111924899A (en) * | 2020-08-11 | 2020-11-13 | 中钢集团南京新材料研究院有限公司 | Method for preparing nickel-cobalt-iron-aluminum-magnesium five-element high-entropy material, product and application |
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