CN109786732A - Multimodal powder based on lithium transition-metal oxide and the application in rechargeable battery - Google Patents
Multimodal powder based on lithium transition-metal oxide and the application in rechargeable battery Download PDFInfo
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- CN109786732A CN109786732A CN201811620929.9A CN201811620929A CN109786732A CN 109786732 A CN109786732 A CN 109786732A CN 201811620929 A CN201811620929 A CN 201811620929A CN 109786732 A CN109786732 A CN 109786732A
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Abstract
The invention discloses a kind of multimodal powder based on lithium transition-metal oxide and the applications in rechargeable battery, preparation method is to mix powder A mono- or two substandard products with mono- substandard products of powder B and/or mono- substandard products of powder C, transition metal oxide or hydroxide mixing is added, at least 500 DEG C at a temperature of, it is sintered under an oxygen-containing atmosphere, obtains multimodal powder of the finished product based on lithium transition-metal oxide.The present invention constitutes multi-peaks structure powder by a variety of particles, forms a kind of positive electrode applied to high fill-ratio stable structure under high voltage.The method of the present invention is simple, and the multimodal material of preparation is made of a variety of particles, better meets filling and requires, improve filling effect, reduce porosity, so that material is obtained higher volume energy density, while having preferably cycle performance.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of multimodal powder based on lithium transition-metal oxide and
Application in rechargeable battery, the powder can be used as the positive electrode of lithium ion battery.
Background technique
Rechargeable lithium ion batteries have the characteristics that power density is big, energy is high and the service life is long, are widely used in 3C neck
Domain.As cobalt acid lithium material utilization amount increases sharply, rechargeable battery safety and energy density are two related problems.
For cobalt acid lithium powder, the factor for influencing density includes the shape of particle, primary particle size and size distribution.
Improving compacted density attenuating porosity can be improved electrode density.Cobalt acid lithium full battery anode is using compacting generally in 3.9-4.2g/
cm3, compacted density raising 0.1g/cm3, the energy density of battery, which also has, significantly to be improved.Cobalt acid lithium electric charge cutoff voltage entirely
Every raising 0.1V, specific capacity will rise 10%.
A variety of different grain size cathode material powder are mutually mixed filling bulky grain gap, reduce porosity, this can increase
Lithium battery energy density, because more active materials are cooperated in the limited bulk of the battery.
Currently, since rechargeable battery safety is insufficient, Li metal can not be used as anode.As a result, the lithium need by
Cathode provides, and which has limited the selections of cathode material.The cathode material is a kind of typical stratiform intercalation material containing lithium.The material
Middle lithium can be passed in and out reversibly.The transition metal oxide of each de- lithium well connects with organic bath during the charging process
Touching, the latter are filled with the hole between these particles.Blanking voltage is improved, cobalt acid lithium loses Li generation phase under high-voltage charge state
Change leads to structural instability, is easy to discharge oxygen with electrolyte effect, cobalt is caused to dissolve out phenomenon, safety is reduced, is being circulated throughout
Cheng Zhong, due to the presence of cobalt dissolution phenomenon, guiding discharge capacity is reduced, so that cycle performance is deteriorated；Pass through what is adulterated and coat
Method reduces contact of the lithium cobaltate cathode material surface with electrolyte, improves security performance.
High volume density is easy to get using relatively large and fine and close particle.It is close that material compacting is improved in cobalt acid lithium
Degree, porosity reduce, and Li diffusion rate slows down, then need to shorten diffusion path inside these particles, this can be reduced
Particle size, or increase material porosity to realize, increasing porosity can make material BET increase, and use the cathode of nanosizing
Material realizes that high density is very difficult.So filling bulky grain gap by miniature and small particle, porosity is reduced, is mentioned
High compacted density, while improving lithium diffusion rate and being very important.
Summary of the invention
The primary purpose of the present invention is that providing a kind of preparation method of multimodal powder based on lithium transition-metal oxide.
Another object of the present invention is to provide multimodal powder prepared by the above method, have at least three quantity granularities
There is high packed density, high rate capability, improvement discharge capacity to have preferable cyclical stability at higher voltages at peak.
Application a further object of the present invention is to provide above-mentioned multimodal powder as rechargeable battery positive electrode.
The purpose of the invention is achieved by the following technical solution:
A kind of preparation method of the multimodal powder based on lithium transition-metal oxide, comprising the following steps:
(1) lithium source, cobalt source are mixed with transition metal oxide or hydroxide powder, Li/Co molar ratio in mixture
It for 0.98-1.08, is sintered under air or oxygen atmosphere, obtains a substandard products of powder A；The partial size of gained powder A is 15-30
μm, preferably 17-26 μm；
In step (1), Li/Co molar ratio preferably 1.05 in mixture；In the transition metal oxide or hydroxide
Transition metal be one or more of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sb or La, transition metal is mixed in step (1)
Total content in object is 1000-10000ppm；
Sintering described in step (1) preferably keeps the temperature 10h or more at not less than 950 DEG C；
(2) lithium source, cobalt source are mixed with transition metal oxide or hydroxide powder, Li/Co molar ratio in mixture
> 1, at least 850 DEG C at a temperature of be sintered in air or oxygen containing atmosphere, obtain a substandard products of powder B；Gained powder B
Partial size is 4-12 μm, preferably 4-6 μm；
In step (2), Li/Co molar ratio preferably 1.02 in mixture；In the transition metal oxide or hydroxide
Transition metal be Y, Al, Mg, Ti, La, F, Ga, Sn, Zr, Fe or Si more than one, transition metal is in step (2) mixture
In total content be 1000-10000ppm；
Sintering described in step (2) preferably keeps the temperature 8h or more at not less than 940 DEG C；
(3) lithium source, cobalt source are mixed with transition metal oxide or hydroxide powder, L/Co molar ratio is in mixture
The mixture is sintered in oxygen-containing atmosphere by 1.00-1.08 at least 800 DEG C of temperature, and oxygen concentration is not less than 15% body in atmosphere
Fraction obtains mono- substandard products of powder C；0.5-4.0 μm of partial size, preferably 1-2 μm of gained powder C；
In step (3), Li/Co molar ratio preferably 1.01 in mixture；In the transition metal oxide or hydroxide
Transition metal be one or more of Ni, Mn, Mg, Al, Y, Yb, Nb, Sn, Cr or Zr, transition metal is in step (3) mixture
In total content be 1000-3000ppm；
Sintering described in step (3) preferably keeps the temperature 6h or more at not less than 880 DEG C；
(4) mono- substandard products of powder A are mixed with mono- substandard products of powder B and/or mono- substandard products of powder C, transition metal oxide is added
Or hydroxide mixing, at least 800 DEG C at a temperature of, be sintered, obtained based on lithium transition-metal oxide under an oxygen-containing atmosphere
Multimodal powder；
Alternatively, mono- substandard products of powder A are obtained A powder second product in 800-980 DEG C of heat preservation 10h or more, then by powder A
Two substandard products are mixed with mono- substandard products of powder B and/or mono- substandard products of powder C, add transition metal oxide or hydroxide, uniformly mixed
Close at least 500 DEG C at a temperature of, be sintered in having oxygen atmosphere, 15% volume fraction of oxygen concentration > in atmosphere；After the completion of sintering,
Obtain the multimodal powder based on lithium transition-metal oxide；
Transition metal in step (4) transition metal oxide or hydroxide is Ni, Mn, Mg, Al, Ti, Yb,
One or more of Nb, Sn, Cr or Zr, transition metal content total in step (4) mix is 1000-10000ppm；
The multimodal powder of step (4) described lithium transition-metal oxide, wherein mono- substandard products of powder A and mono- substandard products of powder B and/
Or the mixing of mono- substandard products of powder C, the weight ratio of three are (12-15): (0-5): (0-2)；
Wherein bis- substandard products of powder A are mixed with mono- substandard products of powder B and/or mono- substandard products of powder C, and the weight ratio of three is (12-
15):(0-5):(0-2)；
In the above method, the lithium source is one of lithium carbonate, lithium hydroxide, lithium acetate, lithium nitrate or lithia
More than, preferably lithium carbonate or lithium hydroxide；The cobalt source is cobaltosic oxide, hydroxide cobalt, cobalt chloride, cobalt nitrate or grass
One or more of sour cobalt, preferably cobaltosic oxide.
In the above-mentioned methods, powder A is once or the ratio of the D50 value of mono- substandard products of D50 value and powder B of two substandard products is greater than 2:
The ratio of the D50 value of mono- substandard products of D50 value and powder C of mono- substandard products of 1, powder B is greater than 4:3；Meanwhile powder A is primary or two substandard products
0.2 ㎡ of specific surface area </g, the specific surface areas of mono- substandard products of powder B is 0.25-0.9 ㎡/g, and the specific surface area of powder C is greater than
0.8㎡/g；The specific surface area is obtained by BET measurement.
Specific surface area is the ratio of surface area/volume, and ratio of the 4 Π r2 than 3/4 Π r3 is (3/r), the bigger 3/r's of particle
It is worth smaller, determines the magnitude range of particle by specific surface area, and the size of particle and compacted density hook, compacted density
It is linked up with again with energy density.
Three groups of powders, which will improve compacted density, must have certain proportion, select suitable proportion that could preferably fill
Bulky grain gap.Because bulky grain clearance space is limited and has magnitude range, medium-sized amounts of particles is too many or granularity is bigger than normal
When, it can be more than bulky grain gap, cannot fill well at this time, so that pressure density declines；Similarly, medium-sized particle it is very little or
Person is too small, can not fill well, prevent gap, from filling up, compacted density can also decline.Molecule is also required to simultaneously
It controls in certain particle size range, because the gap between the gap and medium-sized particle and bulky grain between medium-sized particle needs
Little particle goes to fill, this just equally has certain granularity requirements to molecule.
The powder A finished product is made of inner core and outer layer or inner core, inclusion layer and outer layer, at least has a peak, D50
Partial size is at least 18 μm；
The inner core is made of the lithium and cobalt oxides of containing transition metal ion, has layer structure, and molecular formula is
Li1+a(Co1-xMx)1-aO2, wherein M is one or more of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sb or La, -0.02≤a≤
0.035,0 < x < 0.2；
The outer layer is made of lithium transition-metal oxide, and the molecular formula of the oxide is Li (Co1-zM“z)O2, wherein
M " be one or more of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sr, Cu, Sb or La, z >=0.005；
The inclusion layer is between inner core and outer layer, molecular formula Li1+b(Co1-yM‘y)1-bO2, wherein M ' be Ni,
One or more of Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sr, Cu, Sb or La, -0.01≤b≤0.025,0 < y < 0.06.
There are two types of powder A finished product combinations, the first is internal layer and outer layer, and second is internal layer, inclusion layer and outer layer.
It when one sample is two layers, is burnt generally by one and obtains inner core particles, burnt by two and exist on inner core particles surface
One layer of clad is grown, it is to have any different on ingredient that particle, which reforms into double-layer structure, and inner layer granule and superficial layer, at this time
, it is also distinguishing in the effect of lithium ion battery applications；It is all two burnings in Examples 1 and 2.
One sample one burning is inner layer granule, and two to burn be to grow one layer in internal layer particle surface, be equal to plus one layer namely
Inclusion layer, three burnings are that the surface of particulate inclusion layer is adding one layer of namely outer layer, and powder A finished product is three burnings in embodiment 3；Transition
Metallic element will not volatilize, and adding in few particle will leave how many, the transition adulterated when being sintered by A particle in embodiment 3
The amount of metal oxide can calculate the probable ranges of element in molecular formula.One sample passes through to be sintered three times, three times temperature
Inconsistent, cladding transition metal oxide is variant, and the powder obtained haves three layers.
When a general burning is two peak structure, secondly burning also can be two peak structure.
Preferably, when powder A mono- or two substandard products include bimodal, the D50 value and powder C of powder A mono- or two substandard products are primary
The ratio of the D50 value of product is greater than 6:1, the purpose for the arrangement is that in order to improve compacted density, mono- substandard products powder of A belongs to bulky grain, powder
Mono- substandard products of body C belong to minitype particle, and the D50 ratio between them has to be larger than some value, could fill better.
Preferably, when powder A mono- or two substandard products include bimodal, mono- substandard products of powder A are shared in multimodal powder of the present invention
The ratios of weight fraction of mono- substandard products of weight fraction and powder C be greater than 8:1, the weight fractions of mono- substandard products of powder B and powder C mono-
The ratio of the weight fraction of substandard products is no less than 3:1.
Preferably, when powder A mono- or two substandard products include unimodal, weight powder A shared in multimodal powder of the present invention
The ratio of the weight fraction of mono- substandard products of score and powder C is greater than 6:1.
Mono- substandard products of powder B are the layered crystal structures of Li and material N composition, have at least one peak, D50 partial size
It is 4~12 μm；
The molecular formula of the material N is Co1-mM“‘m, wherein 0 m≤0.07 <, wherein M " ' be Y, Al, Mg, Ti, La, F,
One or more of Ga, Sn, Zr, Fe or Si；
In the powder B, Li/N molar ratio is 0.99-1.02；
When mono- substandard products of powder B include bimodal, the ratio of the D50 value of mono- substandard products of D50 value and powder C of mono- substandard products of powder B
Greater than 2:1；Comprising it is bimodal when, illustrate that this particle is mainly made of the particle of 2 kinds of particle size ranges, each peak represents this
Grain centrostigma.
Mono- substandard products of powder C are that have a no less than peak, partial size≤3 D50 containing lithium cobalt transition metal oxide
μm。
In the present invention, the compacted density for improving cobalt acid lithium is mainly to pass through to improve particle compactness and control cobalt acid lithium
What size distribution was realized.For bulky grain cobalt acid lithium such as particle A, particle is bigger, and the filling of unit volume is bigger, compacted density
Also bigger, but there are many gaps between bulky grain, the presence in gap influences the compacted density of material.Pass through A+B
Grain combination, the combination of A+B+C particle or the combination of A+C particle, to improve compacting, and reach raising volume energy density.
The present invention has the following advantages and effects with respect to the prior art:
It is usually that the compacted density of cobalt acid lithium particle, such as China are improved with the filling of size two kinds of particles specially now with technology
Sharp CN1665052A and CN 105051945B, due to being two kinds of particles filling, filling space is limited, and filling effect is limited, difficult
To obtain best filling effect.
Compared with prior art the present invention has the advantages that the present invention constitutes multi-peaks structure powder by a variety of particles,
Form a kind of positive electrode applied to high fill-ratio stable structure under high voltage.The method of the present invention is simple, the multimodal material of preparation
Material, is made of a variety of particles, is better met filling and is required, improve filling effect, reduces porosity, obtains material higher
Volume energy density, while there is preferably cycle performance.
Detailed description of the invention
Fig. 1 is the granularity distributed number curve of multimodal powder in the embodiment of the present invention 1.
Fig. 2 is the SEM figure of multimodal powder in the embodiment of the present invention 1.
Fig. 3 is the granularity distributed number curve of multimodal powder in the embodiment of the present invention 2.
Fig. 4 is the SEM figure of multimodal powder in the embodiment of the present invention 2.
Fig. 5 is the granularity distributed number curve of multimodal powder in the embodiment of the present invention 3.
Fig. 6 is the SEM figure of multimodal powder in the embodiment of the present invention 3.
Fig. 7 is the granularity distributed number curve of multimodal powder in the embodiment of the present invention 4.
Fig. 8 is the SEM figure of multimodal powder in the embodiment of the present invention 4.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of preparation method of the multimodal powder based on lithium transition-metal oxide, comprising the following steps:
(1) according to Li/Co=1.06 (molar ratio), magnesia (2000ppm containing Mg), aluminium oxide (are contained into Al
2000ppm), four kinds of materials of lithium carbonate and cobaltosic oxide mix 6h in ball mill, and mixture is packed into saggar, is put into stove
Sintering, 5 DEG C/min of heating rate obtain cobalt acid lithium in 1020 DEG C of heat preservation 10h.Cobalt acid lithium obtains bulky grain cobalt acid by being crushed
D50=22 microns of lithium, i.e. mono- substandard products of powder A, at 22 microns, BET is 0.13 ㎡/g at testing graininess only one peak；
(2) in continuous type Co3O4(D50=5 μm), when mixing Li/Co=1.015, by magnesia (containing Mg2000ppm), oxygen
Four kinds of change aluminium (1000ppm containing Al), lithium carbonate and cobaltosic oxide materials mix 6h in ball mill, and mixture is packed into casket
Alms bowl, is put into stove sintering, and 5 DEG C/min of heating rate keeps the temperature 10h, obtain cobalt acid lithium at 970 DEG C.Cobalt acid lithium is obtained by being crushed
To D50=6.5 microns of middle particle cobalt acid lithium, i.e. mono- substandard products of powder B, only one peak of testing graininess is at 6.5 microns；
(3) in continuous type Co3O4(D50=2 μm), when mixing Li/Co=1.01, by magnesia (containing Mg2000ppm), oxygen
Four kinds of change aluminium (500ppm containing Al), lithium carbonate and cobaltosic oxide materials mix 6h in ball mill, and mixture is packed into casket
Alms bowl, is put into stove sintering, and 5 DEG C/min of heating rate keeps the temperature 8h, obtain cobalt acid lithium at 900 DEG C.Cobalt acid lithium is obtained by being crushed
D50=2.5 microns of one substandard products of little particle cobalt acid lithium, i.e. mono- substandard products of powder C, only one peak of testing graininess is at 2.5 microns；
(4) large, medium and small three kinds of particles are mixed according to weight ratio 13:5:2, aluminium oxide (containing Al1000ppm), two is added
Three kinds of particles are mixed 30 minutes mixings in high mixer by titanium oxide (500ppm containing Ti), zirconium oxide (500ppm containing Zr),
8h is fired at 850 DEG C and finally synthesizes positive electrode finished product, which is estimated as Li1.005
Co0.949Mg0.017Al0.024Ti0.005Zr0.005O2, high-voltage-stable type lithium cobaltate cathode material finished product.The cobalt acid lithium powder has three
A quantity distribution of peaks is as shown in Figure 1, SEM is as shown in Figure 2.
0.17 ㎡ of the positive electrode specific surface area/g based on cobalt acid lithium, compacted density 4.11g/cm3.Silver coin type buckles electricity,
In 3.0-4.5V, multiplying power 0.1C, activation cycle N=1, detains electricity head and fill 197.2mAh/g, head puts 190.5mAh/g, head effect
96.6%；Silver coin type is buckled electricity 50 weeks and is recycled, capacity retention ratio 90.6%.
By it is large, medium and small mixing two burning particles and individually a certain kind two burn particle electrical property and compacted density compare as
Shown in the following table 1: after big-and-middle little particle mixing two is burnt, cycle performance is preferably better than single particle within 50 weeks；Compacted density is higher than single
Particle；Cycle performance and compacted density under high pressure can be improved by reasonably controlling big-and-middle short grained weight ratio.
| Number | Head is put | CE% | 50 weeks capacity retention ratios | Compacted density |
| Greatly+in+small | 190.5mAh/g | 96.6% | 90.6% | 4.11g/cm3 |
| Greatly | 188.1mAh/g | 94.6% | 82.1% | 4.03g/cm3 |
| In | 189.2mAh/g | 95.2% | 73.4% | 3.92g/cm3 |
| It is small | 190mAh/g | 95.9% | 52.6% | 3.70g/cm3 |
Embodiment 2
A kind of preparation method of the multimodal powder based on lithium transition-metal oxide, comprising the following steps:
(1) according to Li/Co=1.04 (molar ratio), magnesia (2000ppm containing Mg), aluminium oxide (are contained into Al
3000ppm), four kinds of materials of lithium carbonate and cobaltosic oxide mix 6h in ball mill, and mixture is packed into saggar, is put into stove
Sintering, 5 DEG C/min of heating rate keep the temperature 1h at 750 DEG C, are continuously heating to 1010 DEG C, keep the temperature 10h, obtain cobalt acid lithium.Cobalt acid
Lithium obtains D50=18 micron of bulky grain cobalt acid lithium, i.e. mono- substandard products of powder A by broken, there are two testing graininess quantity peak, and one
A peak is at 7 microns, and at 20 microns, BET is 0.144 ㎡/g at another peak；
(2) in continuous type Co3O4(D50=3 μm), when mixing L/C=1.015, by magnesia (containing Mg2500ppm), oxidation
Four kinds of aluminium (1000ppm containing Al), lithium carbonate and cobaltosic oxide materials mix 6h in ball mill, and mixture is packed into saggar,
It is put into stove sintering, 5 DEG C/min of heating rate keeps the temperature 12h, obtain cobalt acid lithium at 940 DEG C.Cobalt acid lithium is obtained by broken
D50=3.5 microns of particle cobalt acid lithium, i.e. mono- substandard products of powder B, testing graininess is there are two peak, and first peak is at 1.2 microns, and the
Two peaks are at 4.0 microns；
(3) big or middle two kinds of particles are mixed according to weight ratio 3:1, aluminium oxide (1000ppm containing Al), titanium dioxide is added
Three kinds of particles are mixed 30 minutes mixings in high mixer, 880 by (600ppm containing Ti), zirconium oxide (800ppm containing Zr)
8h is fired at DEG C and finally synthesizes high-voltage-stable type lithium cobaltate cathode material finished product.The cobalt acid lithium powder has four quantity point
Cloth peak is as shown in figure 3, SEM is as shown in Figure 4.
The positive electrode specific surface area based on cobalt acid lithium is 0.2 ㎡/g, compacted density 4.05g/cm3.Silver coin type buckles electricity,
In 3.0-4.5V, multiplying power 0.1C, activation cycle N=1, detains electricity head and fill 197.6mAh/g, head puts 191.5mAh/g, head effect
96.9%；Silver coin type is buckled electricity 50 weeks and is recycled, capacity retention ratio 91.2%.
By big-and-middle mixing two burn particle and individually a certain kind two burn particle compare in electrical property and compacted density it is as follows
Shown in table 2: after big-and-middle particle mixing two is burnt, cycle performance and compacted density are higher than single particle；Reasonably control big-and-middle particle
Weight ratio can improve cycle performance and compacted density under high pressure.
| Number | Head is put | CE% | 50 weeks capacity retention ratios | Compacted density |
| Greatly+in | 191.5mAh/g | 96.9% | 91.2% | 4.05g/cm3 |
| Greatly | 187.1mAh/g | 95.1% | 83.3% | 3.92g/cm3 |
| In | 188.2mAh/g | 95.7% | 76.4% | 3.74g/cm3 |
Embodiment 3
A kind of preparation method of the multimodal powder based on lithium transition-metal oxide, comprising the following steps:
(1) according to Li/Co=1.05 (molar ratio), magnesia (2000ppm containing Mg), aluminium oxide (are contained into Al
2000ppm), four kinds of materials of lithium carbonate and cobaltosic oxide mix 6h in ball mill, and mixture is packed into saggar, is put into stove
Sintering, 3 DEG C/min of heating rate keep the temperature 12h, obtain cobalt acid lithium at 1040 DEG C.Cobalt acid lithium obtains bulky grain cobalt by being crushed
Sour D50=17 microns of one substandard products of lithium, only one peak of testing graininess is at 18 microns；It takes a burning cobalt acid lithium that aluminium oxide is added (to contain
Al 1000ppm), titanium dioxide (500ppm containing Ti) ball milling mix, 6h is fired at 800 DEG C and finally to burn cobalts sour for synthesis two
Lithium, i.e. bis- substandard products of powder A, at 21 microns, BET is 0.14 ㎡/g at only one granularity peak
(2) in continuous type Co3O4(D50=3 μm), when mixing L/C=1.015, by magnesia (containing Mg2000ppm), oxidation
Four kinds of aluminium (3000ppm containing Al), lithium carbonate and cobaltosic oxide materials mix 6h in ball mill, and mixture is packed into saggar,
It is put into stove sintering, 5 DEG C/min of heating rate keeps the temperature 12h, obtain cobalt acid lithium at 940 DEG C.Cobalt acid lithium is obtained by broken
D50=4.5 microns of one substandard products of particle cobalt acid lithium, i.e. mono- substandard products of powder B, only one peak of testing graininess is at 4.5 microns；
(3) in continuous type Co3O4(D50=1 μm), when mixing L/C=1.00, by magnesia (containing Mg2000ppm), oxidation
Four kinds of aluminium (500ppm containing Al), lithium carbonate and cobaltosic oxide materials mix 6h in ball mill, and mixture is packed into saggar,
It is put into stove sintering, 5 DEG C/min of heating rate keeps the temperature 6h, obtain cobalt acid lithium at 900 DEG C.Cobalt acid lithium obtains small by being crushed
D50=2.0 microns of one substandard products of particle cobalt acid lithium, i.e. mono- substandard products of powder C, only one peak of testing graininess is at 1.8 microns；
(4) particle in two burning bulky grains, a burning and one being burnt into little particle, three kinds of particles are mixed according to weight ratio 14:5:2,
Aluminium oxide (800ppm containing Al), titanium dioxide (600ppm containing Ti), yttrium oxide (containing Y800ppm) is added, three kinds of particles are existed
High mixer in mix 60 minutes mixings, at 900 DEG C fire 8h and finally synthesize high-voltage-stable type lithium cobaltate cathode material at
Product.The cobalt acid lithium powder has three quantity distribution of peaks as shown in figure 5, SEM is as shown in Figure 6.
The positive electrode surface area based on cobalt acid lithium is 0.18 ㎡/g, compacted density 4.12g/cm3.Silver coin type buckles electricity,
In 3.0-4.5V, multiplying power 0.1C, activation cycle N=1, detains electricity head and fill 198.1mAh/g, head puts 191.7mAh/g, head effect
96.76%；Silver coin type is buckled electricity 50 weeks and is recycled, capacity retention ratio 91.3%.
By it is large, medium and small mixing three burning particles and individually a certain kind two burn particle electrical property and compacted density compare as
Shown in the following table 3: after big-and-middle little particle mixing two is burnt, 50 weeks cycle performances and compacted density are better than single particle；Reasonable control
Big-and-middle short grained weight ratio can improve cycle performance and compacted density under high pressure.
| Number | Head is put | CE% | 50 weeks capacity retention ratios | Compacted density |
| Greatly+in+small | 191.7mAh/g | 96.76% | 91.3% | 4.13g/cm3 |
| Greatly | 188.3mAh/g | 95.0% | 84.4% | 4.05g/cm3 |
| In | 189.7mAh/g | 95.7% | 80.7% | 3.91g/cm3 |
| It is small | 190.4mAh/g | 96.13% | 62.9% | 3.72g/cm3 |
Embodiment 4
A kind of preparation method of the multimodal powder based on lithium transition-metal oxide, comprising the following steps:
(1) according to Li/Co=1.055 (molar ratio), magnesia (2500ppm containing Mg), aluminium oxide (are contained into Al
1500ppm), four kinds of materials of lithium carbonate and cobaltosic oxide mix 5h in ball mill, and mixture is packed into saggar, is put into stove
Sintering, 5 DEG C/min of heating rate keep the temperature 1.5h at 720 DEG C, are continuously heating to 1000 DEG C, keep the temperature 12h, obtain cobalt acid lithium.Cobalt
Sour lithium obtains D50=19.5 microns of bulky grain cobalt acid lithium, i.e. mono- substandard products of powder A, testing graininess has a quantity peak by being crushed
At 19.5 microns, BET is 0.12 ㎡/g；
(2) in continuous type Co3O4(D50=5 μm), when mixing L/C=1.015, by magnesia (containing Mg1500ppm), oxidation
Five kinds of aluminium (2500ppm containing Al), titanium dioxide (1000ppm containing Ti), lithium carbonate and cobaltosic oxide materials are in ball mill
6h is mixed, mixture is packed into saggar, is put into stove sintering, 3 DEG C/min of heating rate keeps the temperature 10h at 950 DEG C, obtains cobalt acid
Lithium.Cobalt acid lithium obtains middle D50=5.5 microns of one substandard products of particle cobalt acid lithium, i.e. mono- substandard products of powder B, testing graininess has by being crushed
One peak is at 5.5 microns；
(3) in continuous type Co3O4(D50=2 μm), when mixing L/C=1.00, by magnesia (containing Mg1500ppm), oxidation
Four kinds of aluminium (500ppm containing Al), lithium carbonate and cobaltosic oxide materials mix 4h in ball mill, and mixture is packed into saggar,
It is put into stove sintering, 2 DEG C/min of heating rate keeps the temperature 8h, obtain cobalt acid lithium at 880 DEG C.Cobalt acid lithium obtains small by being crushed
D50=2.8 microns of one substandard products of particle cobalt acid lithium, i.e. mono- substandard products of powder C, only one peak of testing graininess is at 2.8 microns；
(4) large, medium and small three kinds of particles are mixed according to weight ratio 11:3:1, aluminium oxide (800ppm containing Al), two is added
Titanium oxide (800ppm containing Ti), zirconium oxide (800ppm containing Zr), lanthana (500ppm containing La), three kinds of particles are mixed in height
30 minutes mixings are mixed in loom, and 8h is fired at 870 DEG C and finally synthesize high-voltage-stable type lithium cobaltate cathode material finished product.It should
Cobalt acid lithium powder has four quantity distribution of peaks as shown in fig. 7, SEM is as shown in Figure 8.
The positive electrode specific surface area based on cobalt acid lithium is 0.16 ㎡/g, compacted density 4.15g/cm3.Silver coin type is buckled
Electricity detains electricity head and fills 198.2mAh/g, head puts 191.9mAh/g, head effect in 3.0-4.5V, multiplying power 0.1C, activation cycle N=1
96.8%；Silver coin type is buckled electricity 50 weeks and is recycled, capacity retention ratio 93.3%.
By big-and-middle mixing two burn particle and individually a certain kind two burn particle compare in electrical property and compacted density it is as follows
Shown in table 4: after big-and-middle particle mixing two is burnt, cycle performance and compacted density are higher than single particle；Reasonably control big-and-middle particle
Weight ratio can improve cycle performance and compacted density under high pressure.
| Number | Head is put | CE% | 50 weeks capacity retention ratios | Compacted density |
| Greatly+in+small | 191.9mAh/g | 96.82% | 93.3% | 4.21g/cm3 |
| Greatly | 188.7mAh/g | 95.6% | 88.4% | 4.08g/cm3 |
| In | 187.7mAh/g | 96.2% | 87.7% | 3.80g/cm3 |
| It is small | 192.4mAh/g | 96.36% | 52.6% | 3.68g/cm3 |
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, such as big or middle and little particle difference two burn and burn other multiple sintering situations in mixing three, other any without departing from this hair
Made changes, modifications, substitutions, combinations, simplifications under bright spiritual essence and principle, should be equivalent substitute mode, all wrap
Containing within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the multimodal powder based on lithium transition-metal oxide, it is characterised in that the following steps are included:
(1) lithium source, cobalt source are mixed with transition metal oxide or hydroxide powder, Li/Co molar ratio is in mixture
0.98-1.08 is sintered under air or oxygen atmosphere, obtains mono- substandard products of powder A；The partial size of mono- substandard products of gained powder A is 15-
30μm；
In step (1), transition metal in the transition metal oxide or hydroxide is Ni, Mn, Al, Ti, V, Mg, Y,
One or more of Ce, Zr, Sb or La, total content of the transition metal in step (1) mixture are 1000-10000ppm；
(2) lithium source, cobalt source are mixed with transition metal oxide or hydroxide powder, Li/Co molar ratio > 1 in mixture,
At least 850 DEG C at a temperature of be sintered in air or oxygen containing atmosphere, obtain mono- substandard products of powder B；Mono- substandard products of gained powder B
Partial size is 4-12 μm；
In step (2), transition metal in the transition metal oxide or hydroxide is Y, Al, Mg, Ti, La, F, Ga,
Sn, Zr, Fe or Si more than one, total content of the transition metal in step (2) mixture be 1000-10000ppm；
(3) lithium source, cobalt source are mixed with transition metal oxide or hydroxide powder, L/Co molar ratio is in mixture
The mixture is sintered in oxygen-containing atmosphere by 1.00-1.08 at least 800 DEG C of temperature, and oxygen concentration is not less than 15% body in atmosphere
Fraction obtains mono- substandard products of powder C；Mono- 0.5-4.0 μm of substandard products partial size of gained powder C；
In step (3), transition metal in the transition metal oxide or hydroxide is Ni, Mn, Mg, Al, Y, Yb, Nb,
One or more of Sn, Cr or Zr, total content of the transition metal in step (3) mixture are 1000-3000ppm；
(4) mono- substandard products of powder A are mixed with mono- substandard products of powder B and/or mono- substandard products of powder C, transition metal oxide or hydrogen is added
Oxide mixing, at least 800 DEG C at a temperature of, be sintered, obtained based on the more of lithium transition-metal oxide under an oxygen-containing atmosphere
Peak powder；
Alternatively, one substandard products of powders A are obtained two substandard products of powders A, then by powder A respectively in 800-980 DEG C of heat preservation 10h or more
Two substandard products are mixed with mono- substandard products of powder B and/or mono- substandard products of powder C, add transition metal oxide or hydroxide, uniformly mixed
Close at least 500 DEG C at a temperature of, be sintered in having oxygen atmosphere, 15% volume fraction of oxygen concentration > in atmosphere；After the completion of sintering,
Obtain multimodal powder of the finished product based on lithium transition-metal oxide；
Transition metal in step (4) transition metal oxide or hydroxide is Ni, Mn, Mg, Al, Ti, Yb, Nb, Sn,
One or more of Cr or Zr, total content of the transition metal in step (4) mix is 1000-10000ppm.
2. preparation method according to claim 1, it is characterised in that:
Step (4) is described to mix mono- substandard products of powder A with mono- substandard products of powder B and/or mono- substandard products of powder C, and the weight ratio of three is
(12-15):(0-5):(0-2)；
Step (4) is described to mix bis- substandard products of powder A with mono- substandard products of powder B and/or mono- substandard products of powder C, and the weight ratio of three is
(12-15):(0-5):(0-2)。
3. preparation method according to claim 1, it is characterised in that: the lithium source is lithium carbonate, lithium hydroxide, acetic acid
One or more of lithium, lithium nitrate or lithia.
4. preparation method according to claim 1, it is characterised in that: the cobalt source is cobaltosic oxide, hydroxide
One or more of cobalt, cobalt chloride, cobalt nitrate or cobalt oxalate.
5. a kind of multimodal powder based on lithium transition-metal oxide, it is characterised in that: be as described in claim any one of 1-4
Method be made.
6. multimodal powder according to claim 5, it is characterised in that: be by powder A mono- or two substandard products and mono- substandard products of powder B
And/or mono- substandard products of powder C are sintered.
7. multimodal powder according to claim 6, it is characterised in that: powder A is primary or the D50 value and powder B of two substandard products
The ratio of the D50 value of one substandard products is greater than 2:1, and the ratio of the D50 value of mono- substandard products of D50 value and powder C of mono- substandard products of powder B is greater than 4:
3；Meanwhile powder A is primary or 0.2 ㎡ of specific surface area </g of two substandard products, the specific surface area of mono- substandard products of powder B is 0.25-0.9
The specific surface area of mono- substandard products of ㎡/g, powder C is greater than 0.8 ㎡/g；The specific surface area is obtained by BET device measuring.
8. multimodal powder according to claim 6, it is characterised in that:
The powder A finished product is made of inner core and outer layer, or is made of inner core, inclusion layer and outer layer, at least has one
Peak, D50 partial size are at least 18 μm；
The inner core is made of the lithium and cobalt oxides of containing transition metal ion, has layer structure, molecular formula Li1+a
(Co1-xMx)1-aO2, wherein M is one or more of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sb or La, -0.02≤a≤
0.035,0 < x < 0.2；
The outer layer is made of lithium transition-metal oxide, and the molecular formula of the oxide is Li (Co1-zM“z)O2, M therein
It " is one or more of Ni, Mn, Al, Ti, V, Mg, Y, Ce, Zr, Sr, Cu, Sb or La, z >=0.005；
The inclusion layer is between inner core and outer layer, molecular formula Li1+b(Co1-yM‘y)1-bO2, wherein M ' be Ni, Mn,
One or more of Al, Ti, V, Mg, Y, Ce, Zr, Sr, Cu, Sb or La, -0.01≤b≤0.025,0 < y < 0.06.
9. multimodal powder according to claim 6, it is characterised in that:
Mono- substandard products of powder B are the layered crystal structures of Li and material N composition, have at least one peak, and D50 partial size is 4
~12 μm；
The molecular formula of the material N is Co1-mM“‘m, wherein 0 m≤0.07 <, wherein M " ' be Y, Al, Mg, Ti, La, F, Ga, Sn,
One or more of Zr, Fe or Si；
In mono- substandard products of powder B, Li/N molar ratio is 0.99-1.02；
Mono- substandard products of powder C are that have a no less than peak, partial size≤3 μm D50 containing lithium cobalt transition metal oxide.
10. application of the described in any item multimodal powder of claim 5-9 as rechargeable battery positive electrode.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111931339A (en) * | 2020-07-06 | 2020-11-13 | 清华大学 | Method for determining structural parameters of electrochemical model electrode layer of lithium ion battery |
| CN114927674A (en) * | 2022-06-24 | 2022-08-19 | 合肥融捷能源材料有限公司 | Lithium cobaltate positive electrode material and preparation method and application thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102447107A (en) * | 2011-10-17 | 2012-05-09 | 江苏科捷锂电池有限公司 | High density lithium ion battery cathode material lithium cobalt oxide and preparation method thereof |
| CN102779976A (en) * | 2011-10-10 | 2012-11-14 | 北大先行科技产业有限公司 | Preparation method of cathode material of LCO (lithium cobaltate)-based lithium ion battery |
| CN103022475A (en) * | 2012-12-10 | 2013-04-03 | 彩虹集团电子股份有限公司 | Preparation method for lithium cobalt oxide with high pole piece compaction density |
| CN103066282A (en) * | 2013-01-10 | 2013-04-24 | 东莞新能源科技有限公司 | High-voltage anode material for lithium ion battery and lithium ion battery comprising same |
| CN103682326A (en) * | 2013-12-13 | 2014-03-26 | 南通瑞翔新材料有限公司 | High-capacity lithium cobalt oxide-base lithium ion battery anode material and preparation method thereof |
| CN105051945A (en) * | 2012-12-14 | 2015-11-11 | 尤米科尔公司 | Bimodal lithium transition metal based oxide powder for use in a rechargeable battery |
| CN105449197A (en) * | 2015-12-28 | 2016-03-30 | 中信国安盟固利电源技术有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN107482211A (en) * | 2017-06-15 | 2017-12-15 | 北大先行科技产业有限公司 | A kind of cobalt acid lithium and three element mixing materials and preparation method thereof |
| CN108023068A (en) * | 2017-11-08 | 2018-05-11 | 格林美（无锡）能源材料有限公司 | A kind of 4.40V high voltage types cobalt acid lithium material and preparation method thereof |
| CN108232127A (en) * | 2016-12-15 | 2018-06-29 | 天津国安盟固利新材料科技股份有限公司 | A kind of nucleocapsid cobalt acid lithium material and preparation method thereof |
| CN108269966A (en) * | 2017-12-28 | 2018-07-10 | 国联汽车动力电池研究院有限责任公司 | A kind of method that solid electrode is prepared by cold pressing-material classification grading |
| CN108682850A (en) * | 2018-05-28 | 2018-10-19 | 格林美（无锡）能源材料有限公司 | Micro- rich lithium high-energy density lithium cobaltate cathode material of one kind and preparation method thereof |
-
2018
- 2018-12-28 CN CN201811620929.9A patent/CN109786732B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102779976A (en) * | 2011-10-10 | 2012-11-14 | 北大先行科技产业有限公司 | Preparation method of cathode material of LCO (lithium cobaltate)-based lithium ion battery |
| CN102447107A (en) * | 2011-10-17 | 2012-05-09 | 江苏科捷锂电池有限公司 | High density lithium ion battery cathode material lithium cobalt oxide and preparation method thereof |
| CN103022475A (en) * | 2012-12-10 | 2013-04-03 | 彩虹集团电子股份有限公司 | Preparation method for lithium cobalt oxide with high pole piece compaction density |
| CN105051945A (en) * | 2012-12-14 | 2015-11-11 | 尤米科尔公司 | Bimodal lithium transition metal based oxide powder for use in a rechargeable battery |
| CN103066282A (en) * | 2013-01-10 | 2013-04-24 | 东莞新能源科技有限公司 | High-voltage anode material for lithium ion battery and lithium ion battery comprising same |
| CN103682326A (en) * | 2013-12-13 | 2014-03-26 | 南通瑞翔新材料有限公司 | High-capacity lithium cobalt oxide-base lithium ion battery anode material and preparation method thereof |
| CN105449197A (en) * | 2015-12-28 | 2016-03-30 | 中信国安盟固利电源技术有限公司 | Lithium ion battery cathode material and preparation method thereof |
| CN108232127A (en) * | 2016-12-15 | 2018-06-29 | 天津国安盟固利新材料科技股份有限公司 | A kind of nucleocapsid cobalt acid lithium material and preparation method thereof |
| CN107482211A (en) * | 2017-06-15 | 2017-12-15 | 北大先行科技产业有限公司 | A kind of cobalt acid lithium and three element mixing materials and preparation method thereof |
| CN108023068A (en) * | 2017-11-08 | 2018-05-11 | 格林美（无锡）能源材料有限公司 | A kind of 4.40V high voltage types cobalt acid lithium material and preparation method thereof |
| CN108269966A (en) * | 2017-12-28 | 2018-07-10 | 国联汽车动力电池研究院有限责任公司 | A kind of method that solid electrode is prepared by cold pressing-material classification grading |
| CN108682850A (en) * | 2018-05-28 | 2018-10-19 | 格林美（无锡）能源材料有限公司 | Micro- rich lithium high-energy density lithium cobaltate cathode material of one kind and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111931339A (en) * | 2020-07-06 | 2020-11-13 | 清华大学 | Method for determining structural parameters of electrochemical model electrode layer of lithium ion battery |
| CN111931339B (en) * | 2020-07-06 | 2021-04-23 | 清华大学 | Method for determining structural parameters of electrochemical model electrode layer of lithium ion battery |
| CN114927674A (en) * | 2022-06-24 | 2022-08-19 | 合肥融捷能源材料有限公司 | Lithium cobaltate positive electrode material and preparation method and application thereof |
| CN114927674B (en) * | 2022-06-24 | 2024-03-15 | 合肥融捷能源材料有限公司 | Lithium cobalt oxide positive electrode material, preparation method and application thereof |
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