CN103746111B - A kind of monocrystal nickel cobalt manganese cell positive electrode and preparation method thereof - Google Patents
A kind of monocrystal nickel cobalt manganese cell positive electrode and preparation method thereof Download PDFInfo
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- CN103746111B CN103746111B CN201410042232.3A CN201410042232A CN103746111B CN 103746111 B CN103746111 B CN 103746111B CN 201410042232 A CN201410042232 A CN 201410042232A CN 103746111 B CN103746111 B CN 103746111B
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- 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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- H01M10/05—Accumulators with non-aqueous electrolyte
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Abstract
The present invention relates to a kind of monocrystal nickel cobalt manganese cell positive electrode and preparation method thereof.The invention belongs to technical field of energy material.Monocrystal nickel cobalt manganese cell positive electrode, its chemical formula is LiNi
xco
ymn
1-x-yo
2, wherein, 0.3 & lt; X & lt; 0.8,0.1 & lt; Y & lt; 0.4.The preparation method of monocrystal nickel cobalt manganese cell positive electrode: (1) prepares crystal seed: the carbonate of nickel cobalt manganese or acetate aqueous solution, add concentration 0.5-1.5mol/L ammoniacal liquor; Then the LiOH solution of 1-4mol/L is added; Leave standstill, filter, dry; With LiOHH
2o mixed calcining; (2) prepare presoma: the carbonate of nickel cobalt manganese or acetate aqueous solution, add concentration 0.5-1.5mol/L ammoniacal liquor, add the LiOH solution of 1-4mol/L; Leave standstill, ageing, vacuumize; (3) the obtained monocrystal nickel cobalt manganese cell positive electrode of sintering: lithium source, the crystal seed of presoma and stoichiometric proportion mixs, are compacted into bulk, calcining, cool, pulverizing.The present invention has simple to operate, and granular size easily controls, and particle size distribution is narrow, and product purity is high, cycle performance and the advantage such as security performance is excellent.
Description
Technical field
The invention belongs to technical field of energy material, particularly relate to a kind of monocrystal nickel cobalt manganese cell positive electrode and preparation method thereof.
Background technology
At present, the positive electrode of nickel-cobalt-manganese ternary composite oxide powder is mainly used in the positive electrode of lithium ion battery, has the advantage that other positive electrodes are incomparable.Cobalt acid lithium is due to expensive, and poor safety performance, toxicity is large and be not suitable as power lithium-ion battery positive electrode.LiFePO4 has cheap, and security performance is good, advantages of environment protection, but its energy per volume density is low.It is low that LiMn2O4 has cost, and security performance is better, the advantage that environmental pollution is few, but its cycle performance is poor, and energy per volume density is low.Comparatively speaking, nickel-cobalt-manganternary ternary anode material has that theoretical specific capacity is higher (can reach 275mAg
-1), actual specific capacity can reach 140-180mAg
-1cycle performance is good, and the advantages such as tap density is higher, good thermal stability, can overcome the some drawbacks of other materials.Therefore, one of nickel-cobalt-manganternary ternary anode material preferred material becoming anode material for lithium-ion batteries.
Industrial preparation nickel-cobalt-manganternary ternary anode material LiNi
xco
ymn
1-x-yo
2method mainly contain high temperature solid-state method and liquid phase method.High temperature solid-state method advantage be simple and easy to control, be convenient to realize industrial operation; But it is slow that its shortcoming is ion diffuse speed, and batch mixing is uneven, there is bigger difference in the product of preparation, cause the chemical property of material wayward in composition structure and particle size distribution etc.Liquid phase method application in the industry mainly coprecipitation.Coprecipitation method can make material reach molecule or the mixing of atom level stoichiometric proportion, thus can prepare high-quality battery material with lower production cost, is prepare positive electrode at present to adopt method the most widely.The method can pass through the granularity controlling deposition condition and easy control product, but the bulky grain material of preparation is all often spherical microcrystal grain, is not single crystal grain.Due to the particle heterogeneity that multiple particle is combined into, particle size distribution is wider, and in the process being prepared into battery pole piece, many granules also can come off from large particle surface, and the stability of product is poor.When particularly battery pole piece compacted density is larger, easily spherical microcrystal grain is crushed, cause degradation technical problem under battery quality.
Summary of the invention
The present invention provides a kind of monocrystal nickel cobalt manganese cell positive electrode and preparation method thereof for solving in known technology the technical problem that exists.Consider from the angle of materialogy, use monocrystal material to be optimal selection.Monocrystal has higher mechanical strength, effectively can improve the pressure of pole piece, and pole piece densification is improved.Monocrystal perfect crystalline simultaneously, gram volume increases.In order to obtain monocrystal material, crystal seed can be used as initial nucleator.In synthetic reaction and calcination reaction, add crystal seed, be the technology being applied to Inorganic Non-metallic Materials preparation field, adopts to add the method application that crystal seed method prepares anode material for lithium-ion batteries and to possess skills novelty.
An object of the present invention is to provide one, and to have product purity high, and stability is high, and particle size distribution is narrow, the monocrystal nickel cobalt manganese cell positive electrode of the features such as excellent cycle performance and higher security performance.
The technical scheme that monocrystal nickel cobalt manganese cell positive electrode of the present invention is taked is:
A kind of monocrystal nickel cobalt manganese cell positive electrode, is characterized in: the chemical formula of monocrystal nickel cobalt manganese cell positive electrode is LiNi
xco
ymn
1-x-yo
2, wherein, the span of x is the span of 0.3<x<0.8, y is 0.1<y<0.4.
Two of object of the present invention is to provide a kind of simple to operate, the preparation method of the monocrystal nickel cobalt manganese cell positive electrode of the features such as granular size easily controls, and calcining heat is low, energy savings, and product purity is high, particle size distribution, and function admirable is narrow.
The technical scheme that monocrystal nickel cobalt manganese cell positive electrode of the present invention and preparation method thereof is taked is:
A preparation method for monocrystal nickel cobalt manganese cell positive electrode, is characterized in: the preparation process of monocrystal nickel cobalt manganese cell positive electrode comprises the following steps:
1. prepare crystal seed
The carbonate of nickel cobalt manganese or acetate are mixed with the aqueous solution of concentration 1-4mol/L; Under nitrogen atmosphere and 40-80 DEG C of temperature, stirring condition, in metal salt solution, add the ammoniacal liquor of concentration 0.5-1.5mol/L, ammoniacal liquor (NH
3h
2o) molal quantity is 0.2-3 times of transition metal salt molal quantity, and the ammoniacal liquor joining day is 0.5-2h; Then the LiOH solution of 1-4mol/L is added, until pH value reaches 9-11; Leave standstill 12-20h; 80-140 DEG C of vacuumize 2-10 hour after sediment filters; With LiOHH
2o calcines 4-10h at being blended in 450-550 DEG C, obtains required crystal seed;
2. prepare presoma
The carbonate of nickel cobalt manganese or acetate are mixed with the aqueous solution of concentration 2-4mol/L; Under nitrogen atmosphere and 40-80 DEG C, stirring condition, in metal salt solution, add the ammoniacal liquor of concentration 0.5-1.5mol/L, the addition of ammoniacal liquor is ammoniacal liquor (NH
3h
2o) molal quantity is 0.2-3 times of transition metal salt molal quantity, after reaction 0.5-2h, adds the LiOH solution of 1-4mol/L, until pH value reaches 9-11 in solution; Then 12-20h is left standstill; After ageing, 80-140 DEG C of vacuumize 2-10 hour, obtains described presoma;
3. the obtained monocrystal nickel cobalt manganese cell positive electrode of sintering
After the presoma of gained mixes with the lithium source of stoichiometric proportion, the crystal seed of 0.1-5% weight ratio after dry, be compacted into bulk with forcing press, at 850-950 DEG C of temperature lower calcination 14-24h, cooling, pulverizes, obtains monocrystal nickel cobalt manganese cell positive electrode.
The preparation method of monocrystal nickel cobalt manganese cell positive electrode of the present invention can also adopt following technical scheme:
The preparation method of described monocrystal nickel cobalt manganese cell positive electrode, is characterized in: when preparing crystal seed, and cross 325 mesh sieves after calcining 4-10h, screenings is the required crystal seed obtained.
The preparation method of described monocrystal nickel cobalt manganese cell positive electrode, is characterized in: when forcing press is compacted into bulk, by pressure material thickness be 1-5 centimetre, pressure be 10-50 ton/square metre.
The preparation method of described monocrystal nickel cobalt manganese cell positive electrode, is characterized in: when sintering obtains monocrystal nickel cobalt manganese cell positive electrode, and cross 100-500 mesh sieve after pulverizing, screenings is the monocrystal nickel cobalt manganese cell positive electrode obtained.
The advantage that the present invention has and good effect are:
Monocrystal nickel cobalt manganese cell positive electrode and preparation method thereof is owing to have employed the brand-new technical scheme of the present invention, and compared with prior art, the present invention has simple to operate, and granular size such as easily to control at the advantage.In sintering process, add crystal seed and apply pressure, having and significantly promote that germination becomes the effect of monoclinic crystal structure, and adding crystal seed the temperature of calcining can be made to reduce, energy savings.
Meanwhile, the present invention adopt carbonate or acetate, can decompose completely in sintering process subsequently, can not as sulfate, phosphate the impurity such as residual sulphur, phosphorus.And adopt LiOH as pH value regulator, sodium impurity be can avoid introducing, purity and the performance of product improved.
The nickel-cobalt-manganese ternary battery material of monoclinic crystal structure prepared by the present invention, domain size distribution is at 5-20 μm.Can prevent die break and little crystal grain from coming off in the process preparing battery pole piece, the stability of material is improved.The present invention has broken the fixing thoughtcast of people's synthesis of ternary battery material for a long time, have employed and add the method that crystal seed promotes monoclinic crystal structure growth, prepare one more stable than crystallite agglomerated particle, particle size distribution is narrower, and profile is the preparation method of the nickel-cobalt-manganternary ternary anode material of monoclinic crystal structure.In 3.0V-4.25V voltage range, discharge capacity reaches 160-165mAg first
-1, the pole piece compaction density made can bring up to 3.8g/cm
3above, there is excellent cycle performance and higher security performance.18650 lithium ion batteries that the following material is made can reach the capacity (traditional positive electrode make 18650 lithium ion batteries be generally no more than 2200mAh) of more than 2500mAh.
Accompanying drawing explanation
Fig. 1 is monocrystalline ternary material microstructure figure of the present invention;
Fig. 2 is traditional ternary material microstructure figure.
Two figure contrast material that visible the present invention makes and traditional ternary material has significant difference.
Embodiment
For summary of the invention of the present invention, Characteristic can be understood further, hereby exemplify following examples, and be described with reference to the accompanying drawings as follows:
With reference to accompanying drawing 1.
Embodiment 1
A kind of monocrystal nickel cobalt manganese cell positive electrode, this monocrystal nickel cobalt manganese cell positive electrode is the Li (Ni of 111 types
1/3co
1/3mn
1/3) O
2ternary material.
Embodiment 2
The preparation method of the monocrystal nickel cobalt manganese cell positive electrode described in embodiment 1, comprises following processing step:
(1) first crystal seed is prepared.Take 19.785g nickelous carbonate (nickel content 0.167mol), 19.824g cobalt carbonate (cobalt content 0.167mol), 19.158g manganese carbonate (Fe content 0.167mol) respectively, adding deionized water to solution is 500mL, is mixed with the metal salt solution that concentration is 1mol/L.Under the bath temperature, stirring condition of nitrogen atmosphere and 40 DEG C, quality (is commercially available ammoniacal liquor (the wherein NH of 11.682g by the ammoniacal liquor adding concentration 0.5mol/L in metal salt solution
3h
2o percentage by weight is 30%) add deionized water and be diluted to 200mL, now ammoniacal liquor (NH
3h
2o) molal quantity is 0.1mol, is 0.2 times of transition metal salt molal quantity (0.5mol)).The ammoniacal liquor joining day adds up to 0.5h.Then in solution, the LiOH solution of 1mol/L is added (to the LiOHH of 20.982g
2adding deionized water to solution in O is 500mL), until pH value reaches 9, stop adding LiOH solution.Then 12h is left standstill.80 DEG C of vacuumizes 10 hours after sediment filters, with the LiOHH of 20.982g
2at 450 DEG C, calcine 10h after O mixing, cross 325 mesh sieves, namely screenings is crystal seed of the present invention.
(2) presoma needed for preparation.Take 39.570g nickelous carbonate (nickel content 0.333mol), 39.647g cobalt carbonate (cobalt content 0.333mol), 38.316g manganese carbonate (Fe content 0.333mol) respectively, adding deionized water to solution is 500mL, is mixed with the metal salt solution solution that concentration is 2mol/L.Under the bath temperature, stirring condition of nitrogen atmosphere and 40 DEG C, quality (is ammoniacal liquor (the wherein NH of 23.364g by the ammoniacal liquor adding concentration 0.5mol/L in metal salt solution
3h
2o percentage by weight is 30%) add deionized water and be diluted to 400mL), after reaction 0.5h, in solution, add the LiOH solution of 1mol/L (to the LiOHH of 41.964g
2adding deionized water to solution in O is 1L), until pH value reaches 9, stop adding LiOH solution.Then leave standstill 12h, then 80 DEG C of vacuumize 10 hours, obtains 91.538g presoma of the present invention.
(3) the obtained required battery material of calcining.After after dry, the 91.538g presoma of gained mixes with 36.946g lithium carbonate, 0.128g crystal seed, being compacted into bulk with forcing press (is pressed material thickness to be 1 centimetre, pressure is 10 tons/square metre), at 850 DEG C of temperature lower calcination 24h, cooling, pulverize, cross 100 mesh sieves, namely screenings is positive electrode of the present invention.
Embodiment 3
A kind of monocrystal nickel cobalt manganese cell positive electrode, this monocrystal nickel cobalt manganese cell positive electrode is the Li (Ni of 622 types
0.6co
0.2mn
0.2) O
2ternary material.
Embodiment 4
The preparation method of the monocrystal nickel cobalt manganese cell positive electrode described in embodiment 3, comprises following processing step:
(1) first crystal seed is prepared.Take 45.830g nickel acetate (nickel content 0.300mol), 15.300g cobalt acetate (cobalt content 0.100mol), 14.901g manganese acetate (Fe content 0.100mol) respectively, adding deionized water to solution is 125mL, is mixed with the aqueous solution that concentration is 4mol/L.Under the bath temperature, stirring condition of nitrogen atmosphere and 80 DEG C, quality (is ammoniacal liquor (the wherein NH of 175.228g by the ammoniacal liquor adding concentration 1.5mol/L in metal salt solution
3h
2o percentage by weight is 30%) add deionized water and be diluted to 1L, now ammoniacal liquor (NH
3h
2o) molal quantity is 1.5mol, is 3 times of transition metal salt molal quantity (0.5mol)).The ammoniacal liquor joining day adds up to 2h.Then in solution, the LiOH solution of 4mol/L is added (to the LiOHH of 20.982g
2adding deionized water to solution in O is 125mL), until pH value reaches 11, stop adding LiOH solution.Then 20h is left standstill.140 DEG C of vacuumizes 10 hours after sediment filters, with the LiOHH of 20.982g
2at 550 DEG C, calcine 10h after O mixing, cross 325 mesh sieves, namely screenings is crystal seed of the present invention.
(2) presoma needed for preparation.Take 91.660g nickel acetate (nickel content 0.600mol), 30.600g cobalt acetate (cobalt content 0.200mol), 29.801g manganese acetate (Fe content 0.200mol) respectively, adding deionized water to solution is 250mL, is mixed with the aqueous solution that concentration is 4mol/L.Under the bath temperature, stirring condition of nitrogen atmosphere and 80 DEG C, quality (is ammoniacal liquor (the wherein NH of 350.456g by the ammoniacal liquor adding concentration 1.5mol/L in metal salt solution
3h
2o percentage by weight is 30%) add deionized water and be diluted to 2L), after reaction 2h, in solution, add the LiOH solution of 4mol/L (to the LiOHH of 41.964g
2adding deionized water to solution in O is 250mL), until pH value reaches 11, stop adding LiOH solution.Then 20h is left standstill.After ageing, 140 DEG C of vacuumize 10 hours, obtains 92.009g presoma of the present invention.
(3) the obtained required battery material of calcining.The 92.009g presoma of gained and the LiOHH of 20.982g after dry
2after O, 5.650g crystal seed mixes, be compacted into bulk (pressed material thickness to be 5 centimetres, pressure is 50 tons/square metre) with forcing press, at 950 DEG C of temperature lower calcination 14h, cooling, pulverizes, and cross 500 mesh sieves, namely screenings is positive electrode of the present invention.
Embodiment 5
A kind of monocrystal nickel cobalt manganese cell positive electrode, this monocrystal nickel cobalt manganese cell positive electrode is the Li (Ni of 523 types
0.5co
0.2mn
0.3) O
2ternary material.
Embodiment 6
The preparation method of the monocrystal nickel cobalt manganese cell positive electrode described in embodiment 5, comprises following processing step:
(1) first crystal seed is prepared.Take 29.677g nickelous carbonate (nickel content 0.250mol), 11.894g cobalt carbonate (cobalt content 0.100mol), 17.242g manganese carbonate (Fe content 0.150mol) respectively, adding deionized water to solution is 250mL, is mixed with the aqueous solution that concentration is 2mol/L.Under the bath temperature, stirring condition of nitrogen atmosphere and 60 DEG C, quality (is ammoniacal liquor (the wherein NH of 20.982g by the ammoniacal liquor adding concentration 1mol/L in metal salt solution
3h
2o percentage by weight is 30%) add deionized water and be diluted to 500mL, now ammoniacal liquor (NH
3h
2o) molal quantity is 0.5mol, is 1 times of transition metal salt molal quantity (0.5mol)).After the ammoniacal liquor joining day adds up to 1h.Then in solution, the LiOH solution of 2mol/L is added (to the LiOHH of 20.982g
2adding deionized water to solution in O is 250mL), until pH value reaches 10, stop adding LiOH solution.Then 16h is left standstill.100 DEG C of vacuumizes 6 hours after sediment filters, with the LiOHH of 20.982g
2at 500 DEG C, calcine 6h after O mixing, cross 325 mesh sieves, namely screenings is crystal seed of the present invention.
(2) presoma needed for preparation.Take 59.355g nickelous carbonate (nickel content 0.500mol), 23.788g cobalt carbonate (cobalt content 0.200mol), 34.484g manganese carbonate (Fe content 0.300mol) respectively, adding deionized water to solution is 333mL, is mixed with the aqueous solution that concentration is 3mol/L.Under the bath temperature, stirring condition of nitrogen atmosphere and 60 DEG C, the ammoniacal liquor (be by quality the ammoniacal liquor of 116.189g add deionized water be diluted to 1L) of concentration 1mol/L is added in metal salt solution, after reaction 1h, in solution, add the LiOH solution of 2.5mol/L (to the LiOHH of 41.964g
2adding deionized water to solution in O is 400mL), until pH value reaches 10.5, stop adding LiOH solution.Then 18h is left standstill.After ageing, 120 DEG C of vacuumize 5 hours, obtains 91.633g presoma of the present invention.
(3) the obtained required battery material of calcining.After after dry, the 91.633g presoma of gained mixes with 36.946g lithium carbonate, 2.572g crystal seed, being compacted into bulk with forcing press (is pressed material thickness to be 2 centimetres, pressure is 30 tons/square metre), at 900 DEG C of temperature lower calcination 16h, cooling, pulverize, cross 300 mesh sieves, namely screenings is positive electrode of the present invention.
Preparation method described in the present embodiment is simple to operate, and granular size easily controls, and calcining heat is low, energy savings; It is high that the nickel-cobalt-manganese ternary battery material of monoclinic crystal structure of preparation has stability, and product purity is high, and particle size distribution is narrow, the good effects such as excellent cycle performance and higher security performance.
Claims (4)
1. a preparation method for monocrystal nickel cobalt manganese cell positive electrode, is characterized in that: the chemical formula of monocrystal nickel cobalt manganese cell positive electrode is LiNi
xco
ymn
1-x-yo
2, wherein, the span of x is the span of 0.3<x<0.8, y is 0.1<y<0.4; The preparation process of monocrystal nickel cobalt manganese cell positive electrode comprises the following steps:
(1) crystal seed is prepared
The carbonate of nickel cobalt manganese or acetate are mixed with the aqueous solution of concentration 1-4mol/L; Under nitrogen atmosphere and 40-80 DEG C of temperature, stirring condition, in metal salt solution, add the ammoniacal liquor of concentration 0.5-1.5mol/L, ammoniacal liquor molal quantity be the 0.2-3 of transition metal salt molal quantity doubly, the ammoniacal liquor joining day is 0.5-2h; Then the LiOH solution of 1-4mol/L is added, until pH value reaches 9-11; Leave standstill 12-20h; 80-140 DEG C of vacuumize 2-10 hour after sediment filters; With LiOHH
2o calcines 4-10h at being blended in 450-550 DEG C, obtains required crystal seed;
(2) presoma is prepared
The carbonate of nickel cobalt manganese or acetate are mixed with the aqueous solution of concentration 2-4mol/L; Under nitrogen atmosphere and 40-80 DEG C, stirring condition, in metal salt solution, add the ammoniacal liquor of concentration 0.5-1.5mol/L, ammoniacal liquor molal quantity is 0.2-3 times of transition metal salt molal quantity, after reaction 0.5-2h, the LiOH solution of 1-4mol/L is added, until pH value reaches 9-11 in solution; Then 12-20h is left standstill; After ageing, 80-140 DEG C of vacuumize 2-10 hour, obtains described presoma;
(3) the obtained monocrystal nickel cobalt manganese cell positive electrode of sintering
The presoma of dry rear gained mixes with the lithium source of stoichiometric proportion, crystal seed, the 0.1-5% that the weight of crystal seed is presoma and lithium source weight sum, bulk is compacted into forcing press, at 850-950 DEG C of temperature lower calcination 14-24h, cooling, pulverize, obtain monocrystal nickel cobalt manganese cell positive electrode.
2. the preparation method of monocrystal nickel cobalt manganese cell positive electrode according to claim 1, is characterized in that: when preparing crystal seed, and cross 325 mesh sieves after calcining 4-10h, screenings is the required crystal seed obtained.
3. the preparation method of monocrystal nickel cobalt manganese cell positive electrode according to claim 1, is characterized in that: when forcing press is compacted into bulk, by pressure material thickness be 1-5 centimetre, pressure be 10-50 ton/square metre.
4. the preparation method of monocrystal nickel cobalt manganese cell positive electrode according to claim 1, it is characterized in that: when sintering obtains monocrystal nickel cobalt manganese cell positive electrode, cross 100-500 mesh sieve after pulverizing, screenings is the monocrystal nickel cobalt manganese cell positive electrode obtained.
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| DE102017207683A1 (en) * | 2016-05-09 | 2017-11-09 | Nichia Corporation | A process for producing a nickel-cobalt composite hydroxide and a process for producing an active material of a positive electrode for an anhydrous electrolyte secondary battery |
| CN106910882B (en) * | 2017-04-01 | 2019-04-23 | 济南大学 | A kind of preparation method of lithium ion battery large single crystal layered cathode material |
| CN107565125B (en) | 2017-08-25 | 2019-10-29 | 湖南杉杉能源科技股份有限公司 | A kind of high voltage precursor of nickel-cobalt-lithium-manganese-oxide and preparation method thereof and high voltage nickel-cobalt lithium manganate cathode material |
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