CN107482211A - A kind of cobalt acid lithium and three element mixing materials and preparation method thereof - Google Patents
A kind of cobalt acid lithium and three element mixing materials and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of cobalt acid lithium and three element mixing materials and preparation method thereof, and using solid phase mixing, the method for sintering synthesis, the cobalt acid lithium of specified particle size and three elements are prepared into mixing material in accordance with the appropriate ratio.The preparation method that the present invention uses is low to Preparation equipment requirement, but the mixing material prepared has high compacted density (4.40g/cm3More than), there is more preferable security performance under 4.5V even more high voltages.
Description
Technical field
The invention belongs to lithium ion battery electrode material field, is related to a kind of cobalt acid lithium and three element mixing materials and its system
Preparation Method.
Background technology
Cobalt acid lithium and three elements are current the most abundant, the most widely used consumer lithium ion cell positive materials of research
Material.In recent years, the operating voltage more and more higher of consumer lithium ion battery, volume energy density, security to positive electrode
Can etc. requirement also more and more higher.Cobalt acid lithium has higher compacted density and energy density, but poor safety performance, cost of material
It is high.Three elements have preferable security performance and relatively low cost of material, but compacted density and energy density are low.Single cobalt acid
Lithium or three elements can not fully meet every demand in market.
By controlling the granularity of both positive electrodes, its performance can be improved to a certain extent.For example, increase cobalt acid
The particle diameter of lithium can improve its security performance, reduce the particle diameter of three elements and can improve its energy efficiency.But this method pair
The improvement of material property is limited.
The content of the invention
It is an object of the invention to provide a kind of cobalt acid lithium and three element mixing materials and preparation method thereof, mixed using solid phase
Close, the method preparation of sintering synthesis, make mixing material prepared by the present invention that there is high compacted density (4.40g/cm3More than),
There is more preferable security performance under 4.5V even more high voltages.
To achieve these goals, the present invention uses following technical scheme：
A kind of cobalt acid lithium and three element mixing materials, are made up of cobalt acid lithium monocrystalline bulky grain and three element little particles, and it is changed
Formula is (1-x) Li1+aCo1-bMbO2·xLi1+cNidCoeMnfM'gO2, wherein, Li1+aCo1-bMbO2Represent big of cobalt acid lithium monocrystalline
Grain, its particle size range are 16≤D50≤21 μm, 0≤a≤0.1,0<B≤0.1, M be Mg, Ca, Cu, Ni, B, Al, Cr, Fe, Ti,
One or more in Mn, Zr, V, Nb, Mo, W；Li1+cNidCoeMnfM'gO2Three element little particles are represented, according to Horsfield
It is 0 that model [2], which calculates its particle size range,<D50<9 μm, 0≤c≤0.1,0.1≤d≤0.8,0.1≤e≤0.8,0≤f≤
0.1,0≤g≤0.1, M' are the one or more in Mg, Ca, Cu, B, Al, Cr, Fe, Ti, Zr, V, Nb, Mo, W；Wherein x is three
The short grained weight of element accounts for the percentage of the gross weight of cobalt acid lithium and three element mixing materials, and 0<x≤0.5.
Further, the short grained particle diameter of three elements is according to the particle diameter and Horsfield of the cobalt acid lithium bulky grain
Model is calculated.
Further, the particle size range of above-mentioned cobalt acid lithium and three element mixing materials is 10≤D50≤20 μm, preferably 13≤
D50≤17μm。
Further, the preparation method of described cobalt acid lithium and three element mixing materials has three kinds：One kind is a solid phase
Mixed sintering；One kind is that solid phase mixing sinters twice；One kind is to sinter solid phase mixing respectively.
The method of solid phase mixing sintering cobalt acid lithium and three element mixing materials is as follows：
1) by the molar ratio weighing lithium source of element shown in the chemical formula of cobalt acid lithium and three element mixing materials, cobalt precursor
Body, ternary
The auxiliary material of plain presoma, the auxiliary material containing M element and the element containing M', solid phase mixing are uniform.
2) by the mixed powder obtained in step 1) in 700~1100 DEG C of calcinings, soaking time is 2~10 hours, natural
Cooling
Sieving obtains cobalt acid lithium and three element mixing materials afterwards.
Lithium source described in step 1) is the mixture of one or both of lithium carbonate and lithium hydroxide, the cobalt precursor
It is one or more mixtures in cobaltosic oxide, hydroxy cobalt oxide, cobalt hydroxide and cobalt carbonate, the three elements forerunner
Body is one or more mixtures in oxide, oxyhydroxide, hydroxide and the carbonate of the element containing Ni/Co/Mn,
The auxiliary material containing M element is the one or more in M oxide, hydroxide, acetate, carbonate, subcarbonate
Mixture, the auxiliary material of the element containing M' is in M oxide, hydroxide, acetate, carbonate, subcarbonate
One or more mixtures.
Preferably, calcining heat described in step 2) is 850~1100 DEG C.
Solid phase mixing sintering prepares cobalt acid lithium twice and the method for three element mixing materials is as follows：
1) the molar ratio weighing cobalt precursor of element shown in the chemical formula by cobalt acid lithium and the auxiliary material containing M element, solid phase
Mixing
Uniformly.
2) elemental precursor of molar ratio weighing three of element and the auxiliary material of the element containing M' shown in the chemical formula by three elements,
Solid phase is mixed
Close uniform.
3) body containing cobalt powder obtained in lithium source, step 1) and step are weighed by the chemical formula of cobalt acid lithium and three element mixing materials
It is rapid 2)
In obtain contain three element powders, solid phase mixing is uniform, then 700~1100 DEG C calcining, soaking time be 2~
10 hours,
Sieving obtains cobalt acid lithium and three element mixing materials after natural cooling.
In step 1) the cobalt precursor be in cobaltosic oxide, hydroxy cobalt oxide, cobalt hydroxide and cobalt carbonate one
Kind or a variety of mixtures, the auxiliary material containing M element are M oxide, hydroxide, acetate, carbonate, basic carbonates
One or more mixtures in salt.
Three elemental precursors described in step 2) are oxide, oxyhydroxide, the hydroxide of the element containing Ni/Co/Mn
With one or more mixtures in carbonate, the auxiliary material of the element containing M' is M' oxide, hydroxide, acetic acid
One or more mixtures in salt, carbonate, subcarbonate.
Lithium source described in step 3) is the mixture of one or both of lithium carbonate and lithium hydroxide.
Preferably, calcining heat described in step 3) is 850~1100 DEG C.
The method for sintering solid phase mixing preparation cobalt acid lithium and three element mixing materials respectively is as follows：
1) molar ratio weighing lithium source, cobalt precursor and the auxiliary material containing M element of element shown in the chemical formula by cobalt acid lithium,
Solid phase mixing is uniform, is then 2~10 hours in 850~1100 DEG C of calcinings, soaking time, is sieved after natural cooling and obtain cobalt acid
Lithium monocrystalline bulky grain.
2) the molar ratio weighing lithium source of element shown in the chemical formula of three elements, three elemental precursors and the element containing M ' are pressed
Auxiliary material, solid phase mixing is uniform, is then 2~10 hours in 700~1100 DEG C of calcinings, soaking time, is sieved after natural cooling
To three element little particles.
3) big of the cobalt acid lithium monocrystalline that will be obtained in step 1) is weighed by the chemical formula of cobalt acid lithium and three element mixing materials
The three element little particles obtained in grain and step 2), solid phase mixing is uniform, obtains cobalt acid lithium and three element mixing materials.
Lithium source described in step 1) is the mixture of one or both of lithium carbonate and lithium hydroxide, the cobalt precursor
It is one or more mixtures in cobaltosic oxide, hydroxy cobalt oxide, cobalt hydroxide and cobalt carbonate, it is described containing M element
Auxiliary material is one or more mixtures in M oxide, hydroxide, acetate, carbonate, subcarbonate.
Lithium source described in step 2) is the mixture of one or both of lithium carbonate, lithium hydroxide, before three element
It is one or more mixing in oxide, oxyhydroxide, hydroxide and the carbonate of the element containing Ni/Co/Mn to drive body
Thing, the auxiliary material of the element containing M' be M' oxide, hydroxide, acetate, carbonate, one kind in subcarbonate or
A variety of mixtures.
Preferably, calcining heat described in step 1) is 950~1100 DEG C, calcining heat described in step 2) is 750~
1000℃。
Preferably, the particle size range of the bulky grain of cobalt acid lithium monocrystalline described in step 1) is 18≤D50≤21 μm, in step 2)
The short grained particle size range of three elements is 1≤D50≤5 μm.
The present invention is close according to the performance of cobalt acid lithium monocrystalline bulky grain and three element little particle both positive electrodes, powder
Model (Wu Chengbao, Hu little Fang, the Duan Baitao of accumulation.The theoretical calculation of powder bulk density, Chinese powder science and technology, 2009,15
(5)：76-81；Niu Quanlin, Zhang Minghui, Han Dong, Jia Tianyi.The analysis of mineral superfine powder filling effect, national high performance concrete
Seminar, 2002), preferably go out the particle size range that both positive electrodes most match between each other.Because theoretical model assumes powder
Body is the completely the same positive spheroid of the smooth particle diameter in surface, and actual powder is that shaggy particle size distribution is larger
Irregular particle, it is also necessary to according to the compacted density result actually measured, preferably go out the optimum weight ratio of both positive electrodes
Example.In mixing material, cobalt acid lithium bulky grain can improve compacted density and energy density, and three element little particles can fill cobalt
Gap between sour lithium bulky grain, further improves compacted density, while improve security performance.Therefore, by the cobalt of specified particle size
Sour lithium and three elements prepare mixing material in accordance with the appropriate ratio, and the advantages of can preferably playing both materials each is simultaneously
Shortcoming is avoided, so that cobalt acid lithium and three element mixing materials have high compacted density, is had under 4.5V even more high voltages
More preferable security performance.
Method provided by the invention, which need to only pass through solid phase mixing and heat, can obtain cobalt acid lithium and the mixing of three elements
Material, low is required to Preparation equipment, the compacted density and security performance of this mixing material be substantially better than single cobalt acid lithium and
Three element products.
Brief description of the drawings
Fig. 1 (a) represents the field emission scanning electron microscope photo of cobalt acid lithium monocrystalline bulky grain, and Fig. 1 (b) represents that 523 is small
The field emission scanning electron microscope photo of particle, Fig. 1 (c) represent cobalt acid lithium and three element mixing materials prepared by embodiment 4
Field emission scanning electron microscope photo, Fig. 1 (d) represent embodiment 5 prepare cobalt acid lithium and three element mixing materials field
Launch electron scanning micrograph, Fig. 1 (e) represents the cobalt acid lithium of the preparation of embodiment 6 and the Flied emission of three element mixing materials
Electron scanning micrograph；
Fig. 2 is cobalt acid lithium monocrystalline bulky grain, 523 little particles, cobalt acid lithium and the ternary that in the present invention prepared by embodiment 4,5,6
3.0~4.5V in half-cell of plain mixing material is by specific capacity-voltage curve obtained by 0.1C/0.1C charge-discharge tests；
Fig. 3 is cobalt acid lithium monocrystalline bulky grain, 523 little particles, cobalt acid lithium and the ternary that in the present invention prepared by embodiment 4,5,6
3.0~4.6V in half-cell of plain mixing material is by specific capacity-voltage curve obtained by 0.1C/0.1C charge-discharge tests；
Fig. 4 is cobalt acid lithium monocrystalline bulky grain, 523 little particles, cobalt acid lithium and three element mixing materials prepared by embodiment 4,5,6
Expect the circulation volume conservation rate curve of the 4.5V/0.7C in half-cell；
Fig. 5 is cobalt acid lithium monocrystalline bulky grain, 523 little particles, cobalt acid lithium and three element mixing materials prepared by embodiment 4,5,6
Expect the circulation volume conservation rate curve of the 4.6V/0.7C in half-cell；
Fig. 6 is cobalt acid lithium monocrystalline bulky grain, 523 little particles, cobalt acid lithium and three element mixing materials prepared by embodiment 4,5,6
Expect the thermal analysis curve in half-cell under 4.5V Charging states.
Embodiment
Explanation is of the invention by way of examples below, but is not construed as limiting the invention.
Embodiment 1
Design Li1.08Co0.90Al0.10O2Average D50=19.4 μm of bulky grain.It is calculated according to Horsfield models
Li1.02Ni0.33Co0.33Mn0.33W0.01O2Short grained average D50 scopes are 0~8.0 μm, design
Li1.02Ni0.33Co0.33Mn0.33W0.01O2It is short grained average D50=8.0 μm.
According to chemical formula Li108Co090Al010O2Mol ratio weigh hydroxy cobalt oxide and nano-aluminium oxide is placed in ball
In grinding jar, the mass ratio of ball material is 2:1, ball milling 3 hours, it is well mixed.
According to chemical formula Li1.02Ni0.33Co0.33Mn0.33W0.01O2Mol ratio weigh three element hydroxide and metatungstic acid
Ammonium is placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 3 hours, it is well mixed.
According to chemical formula 0.50Li1.08Co0.90Al0.10O2·0.50Li1.02Ni0.33Co0.33Mn0.33W0.01O2Weigh carbonic acid
Lithium, the mixed powder containing cobalt and the mixed powder containing three elements, are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 4 is small
When, it is well mixed.Calcined mixed powder, calcining heat are 1000 DEG C, and soaking time is 8 hours, and 300 mesh sieves are crossed after natural cooling
Cobalt acid lithium and three element mixing materials are obtained, it is average D50=17.0 μm.
Embodiment 2
Design Li1.08Co0.90Al0.10O2Average D50=19.4 μm of bulky grain.It is calculated according to Horsfield models
Li1.02Ni0.33Co0.33Mn0.33W0.01O2Short grained average D50 scopes are 0~8.0 μm, design
Li1.02Ni0.33Co0.33Mn0.33W0.01O2It is short grained average D50=8.0 μm.
According to chemical formula Li1.08Co0.90Al0.10O2Mol ratio weigh hydroxy cobalt oxide and nano-aluminium oxide is placed in
In ball grinder, the mass ratio of ball material is 2:1, ball milling 3 hours, it is well mixed.
According to chemical formula Li1.02Ni0.33Co0.33Mn0.33W0.01O2Mol ratio weigh three element hydroxide and metatungstic acid
Ammonium is placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 3 hours, it is well mixed.
According to chemical formula 0.60Li1.08Co0.90Al0.10O2·0.40Li1.02Ni0.33Co0.33Mn0.33W0.01O2Weigh carbonic acid
Lithium, the mixed powder containing cobalt and the mixed powder containing three elements, are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 4 is small
When, it is well mixed.Calcined mixed powder, calcining heat are 1000 DEG C, and soaking time is 8 hours, and 300 mesh sieves are crossed after natural cooling
Cobalt acid lithium and three element mixing materials are obtained, it is average D50=17.5 μm.
Embodiment 3
Design Li1.08Co0.90Al0.10O2Average D50=19.4 μm of bulky grain.It is calculated according to Horsfield models
Li1.02Ni0.33Co0.33Mn0.33W0.01O2Short grained average D50 scopes are 0~8.0 μm, design
Li1.02Ni0.33Co0.33Mn0.33W0.01O2It is short grained average D50=8.0 μm.
According to chemical formula Li1.08Co0.90Al0.10O2Mol ratio weigh hydroxy cobalt oxide and nano-aluminium oxide is placed in
In ball grinder, the mass ratio of ball material is 2:1, ball milling 3 hours, it is well mixed.
According to chemical formula Li1.02Ni0.33Co0.33Mn0.33W0.01O2Mol ratio weigh three element hydroxide and metatungstic acid
Ammonium is placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 3 hours, it is well mixed.
According to chemical formula 0.70Li1.08Co0.90Al0.10O2·0.30Li1.02Ni0.33Co0.33Mn0.33W0.01O2Weigh carbonic acid
Lithium, the mixed powder containing cobalt and the mixed powder containing three elements, are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 4 is small
When, it is well mixed.Calcined mixed powder, calcining heat are 1000 DEG C, and soaking time is 8 hours, and 300 mesh sieves are crossed after natural cooling
Cobalt acid lithium and three element mixing materials are obtained, it is average D50=17.9 μm.
Embodiment 4
According to chemical formula Li1.05Co0.97Mg0.005Al0.02Ti0.005O2Mol ratio weigh lithium carbonate, cobaltosic oxide, alkali
Formula magnesium carbonate, nano-aluminium oxide and nano titanium oxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 is small
When, it is well mixed.Calcined mixed powder, calcining heat are 1050 DEG C, and soaking time is 10 hours, and 300 mesh are crossed after natural cooling
Sieve obtains 100g cobalt acid lithium monocrystalline bulky grain, average D50=19.4 μm.
Li is calculated according to Horsfield models1.04Ni0.50Co0.20Mn0.28Zr0.02O2Short grained average D50 scopes
It is 0~8.0 μm, designs Li1.04Ni0.50Co0.20Mn0.28Zr0.02O2It is short grained average D50=4.2 μm.
According to chemical formula Li1.04Ni0.50Co0.20Mn0.28Zr0.02O2Mol ratio weigh lithium hydroxide, three element hydroxides
Thing and nano zirconium dioxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcined mixed powder
Body, calcining heat are 850 DEG C, and soaking time is 6 hours, and 400 mesh sieves are crossed after natural cooling and obtain 50g 523 little particles.
According to chemical formula 0.67Li1.05Co0.97Mg0.005Al0.02Ti0.005O2·
0.33Li1.04Ni0.50Co0.20Mn0.28Zr0.02O2, weigh cobalt acid lithium monocrystalline bulky grain and the common 100g of 523 little particles, ball milling mixing 4
Hour, cobalt acid lithium and three element mixing materials are obtained, it is average D50=14.4 μm.
Embodiment 5
According to chemical formula Li1.05Co0.97Mg0.005Al0.02Ti0.005O2Mol ratio weigh lithium carbonate, cobaltosic oxide, alkali
Formula magnesium carbonate, nano-aluminium oxide and nano titanium oxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 is small
When, it is well mixed.Calcined mixed powder, calcining heat are 1050 DEG C, and soaking time is 10 hours, and 300 mesh are crossed after natural cooling
Sieve obtains 100g cobalt acid lithium monocrystalline bulky grain, average D50=19.4 μm.
Li is calculated according to Horsfield models1.04Ni0.50Co0.20Mn0.28Zr0.02O2Short grained average D50 scopes
It is 0~8.0 μm, designs Li1.04Ni0.50Co0.20Mn0.28Zr0.02O2It is short grained average D50=4.2 μm.
According to chemical formula Li1.04Ni0.50Co0.20Mn0.28Zr0.02O2Mol ratio weigh lithium hydroxide, three element hydroxides
Thing and nano zirconium dioxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcined mixed powder
Body, calcining heat are 850 DEG C, and soaking time is 6 hours, and 400 mesh sieves are crossed after natural cooling and obtain 50g 523 little particles.
According to chemical formula 0.75Li1.05Co0.97Mg0.005Al0.02Ti0.005O2·
0.25Li1.04Ni0.50Co0.20Mn0.28Zr0.02O2, weigh cobalt acid lithium monocrystalline bulky grain and the common 100g of 523 little particles, ball milling mixing 4
Hour, cobalt acid lithium and three element mixing materials are obtained, it is average D50=15.5 μm.
Embodiment 6
According to chemical formula Li1.05Co0.97Mg0.005Al0.02Ti0.005O2Mol ratio weigh lithium carbonate, cobaltosic oxide, alkali
Formula magnesium carbonate, nano-aluminium oxide and nano titanium oxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 is small
When, it is well mixed.Calcined mixed powder, calcining heat are 1050 DEG C, and soaking time is 10 hours, and 300 mesh are crossed after natural cooling
Sieve obtains 100g cobalt acid lithium monocrystalline bulky grain, average D50=19.4 μm.
Li is calculated according to Horsfield models1.04Ni0.50Co0.20Mn0.28Zr0.02O2Short grained average D50 scopes
It is 0~8.0 μm, designs Li1.04Ni0.50Co0.20Mn0.28Zr0.02O2It is short grained average D50=4.2 μm.
According to chemical formula Li1.04Ni0.50Co0.20Mn0.28Zr0.02O2Mol ratio weigh lithium hydroxide, three element hydroxides
Thing and nano zirconium dioxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcined mixed powder
Body, calcining heat are 850 DEG C, and soaking time is 6 hours, and 400 mesh sieves are crossed after natural cooling and obtain 50g 523 little particles.
According to chemical formula 0.80Li1.05Co0.97Mg0.005Al0.02Ti0.005O2·
0.20Li1.04Ni0.50Co0.20Mn0.28Zr0.02O2, weigh cobalt acid lithium monocrystalline bulky grain and the common 100g of 523 little particles, ball milling mixing 4
Hour, cobalt acid lithium and three element mixing materials are obtained, it is average D50=16.3 μm.
Embodiment 7
Design Li1.00Co0.98Mg0.01Zr0.01O2Average D50=16.0 μm of bulky grain.Calculated according to Horsfield models
Draw Li1.07Ni0.59Mg0.01Co0.20Mn0.19Zr0.01O2Short grained average D50 scopes are 0~6.6 μm, design
Li1.07Ni0.59Mg0.01Co0.20Mn0.19Zr0.01O2It is short grained average D50=4.2 μm.
According to chemical formula 0.70Li1.00Co0.98Mg0.01Zr0.01O2·
0.30Li1.07Ni0.59Mg0.01Co0.20Mn0.19Zr0.01O2Mol ratio weigh lithium carbonate, cobaltosic oxide, three element hydroxides
Thing, basic magnesium carbonate and nano zirconium dioxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.
Calcined mixed powder, calcining heat are 950 DEG C, and soaking time is 6 hours, and 300 mesh sieves are crossed after natural cooling and obtain 100g cobalt
Sour lithium and three element mixing materials, it is average D50=12.8 μm.
Embodiment 8
Design Li1.00Co0.98Mg0.01Zr0.01O2Average D50=16.0 μm of bulky grain.Calculated according to Horsfield models
Draw Li1.07Ni0.59Mg0.01Co0.20Mn0.19Zr0.01O2Short grained average D50 scopes are 0~6.6 μm, design
Li1.07Ni0.59Mg0.01Co0.20Mn0.19Zr0.01O2It is short grained average D50=4.2 μm.
According to chemical formula 0.80Li1.00Co0.98Mg0.01Zr0.01O2·
0.20Li1.07Ni0.59Mg0.01Co0.20Mn0.19Zr0.01O2Mol ratio weigh lithium carbonate, cobaltosic oxide, three element hydroxides
Thing, basic magnesium carbonate and nano zirconium dioxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.
Calcined mixed powder, calcining heat are 950 DEG C, and soaking time is 6 hours, and 300 mesh sieves are crossed after natural cooling and obtain 100g cobalt
Sour lithium and three element mixing materials, it is average D50=13.6 μm.
Embodiment 9
Design Li1.00Co0.98Mg0.01Zr0.01O2Average D50=16.0 μm of bulky grain.Calculated according to Horsfield models
Draw Li1.07Ni0.59Mg0.01Co0.20Mn0.19Zr0.01O2Short grained average D50 scopes are 0~6.6 μm, design
Li1.07Ni0.59Mg0.01Co0.20Mn0.19Zr0.01O2It is short grained average D50=4.2 μm.
According to chemical formula 0.90Li1.00Co0.98Mg0.01Zr0.01O2·
0.10Li1.07Ni0.59Mg0.01Co0.20Mn0.19Zr0.01O2Mol ratio weigh lithium carbonate, cobaltosic oxide, three element hydroxides
Thing, basic magnesium carbonate and nano zirconium dioxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.
Calcined mixed powder, calcining heat are 950 DEG C, and soaking time is 6 hours, and 300 mesh sieves are crossed after natural cooling and obtain 100g cobalt
Sour lithium and three element mixing materials, it is average D50=14.3 μm.
Embodiment 10
According to chemical formula Li1.03Co0.94Ni0.03Al0.02Mn0.01O2Mol ratio weigh lithium carbonate, cobaltosic oxide, nanometer
Nickel oxide, nano-aluminium oxide and nano-manganese dioxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours,
It is well mixed.Calcined mixed powder, calcining heat are 1100 DEG C, and soaking time is 8 hours, and 300 mesh sieves are crossed after natural cooling and are obtained
It is average D50=16.0 μm to 100g cobalt acid lithium monocrystalline bulky grain.
Li is calculated according to Horsfield models1.10Ni0.80Co0.10Mn0.09Ti0.01O2Short grained average D50 scopes
It is 0~6.6 μm, designs Li1.10Ni0.80Co0.10Mn0.09Ti0.01O2It is short grained average D50=2.0 μm.
According to chemical formula Li1.10Ni0.80Co0.10Mn0.09Ti0.01O2Mol ratio weigh lithium hydroxide, three element hydroxides
Thing and nano titanium oxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcined mixed powder
Body, calcining heat are 900 DEG C, and soaking time is 4 hours, and 400 mesh sieves are crossed after natural cooling and obtain 50g 811 little particles.
According to chemical formula 0.67Li1.03Co0.94Ni0.03Al0.02Mn0.01O2·
0.33Li1.10Ni0.80Co0.10Mn0.09Ti0.01O2, weigh cobalt acid lithium monocrystalline bulky grain and the common 100g of 811 little particles, ball milling mixing 2
Hour, cobalt acid lithium and three element mixing materials are obtained, it is average D50=11.7 μm.
Embodiment 11
According to chemical formula Li1.03Co0.94Ni0.03Al0.02Mn0.01O2Mol ratio weigh lithium carbonate, cobaltosic oxide, nanometer
Nickel oxide, nano-aluminium oxide and nano-manganese dioxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours,
It is well mixed.Calcined mixed powder, calcining heat are 1100 DEG C, and soaking time is 8 hours, and 300 mesh sieves are crossed after natural cooling and are obtained
It is average D50=16.0 μm to 100g cobalt acid lithium monocrystalline bulky grain.
Li is calculated according to Horsfield models1.10Ni0.80Co0.10Mn0.09Ti0.01O2Short grained average D50 scopes
It is 0~6.6 μm, designs Li1.10Ni0.80Co0.10Mn0.09Ti0.01O2It is short grained average D50=2.0 μm.
According to chemical formula Li1.10Ni0.80Co0.10Mn0.09Ti0.01O2Mol ratio weigh lithium hydroxide, three element hydroxides
Thing and nano titanium oxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcined mixed powder
Body, calcining heat are 900 DEG C, and soaking time is 4 hours, and 400 mesh sieves are crossed after natural cooling and obtain 50g 811 little particles, average
D50=2.0 μm.
According to chemical formula 0.75Li1.03Co0.94Ni0.03Al0.02Mn0.01O2·
0.25Li1.10Ni0.80Co0.10Mn0.09Ti0.01O2, weigh cobalt acid lithium monocrystalline bulky grain and the common 100g of 811 little particles, ball milling mixing 2
Hour, cobalt acid lithium and three element mixing materials are obtained, it is average D50=13.0 μm.
Embodiment 12
According to chemical formula Li1.03Co0.94Ni0.03Al0.02Mn0.01O2Mol ratio weigh lithium carbonate, cobaltosic oxide, nanometer
Nickel oxide, nano-aluminium oxide and nano-manganese dioxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours,
It is well mixed.Calcined mixed powder, calcining heat are 1100 DEG C, and soaking time is 8 hours, and 300 mesh sieves are crossed after natural cooling and are obtained
It is average D50=16.0 μm to 100g cobalt acid lithium monocrystalline bulky grain.
Li is calculated according to Horsfield models1.10Ni0.80Co0.10Mn0.09Ti0.01O2Short grained average D50 scopes
It is 0~6.6 μm, designs Li1.10Ni0.80Co0.10Mn0.09Ti0.01O2It is short grained average D50=2.0 μm.
According to chemical formula Li1.10Ni0.80Co0.10Mn0.09Ti0.01O2Mol ratio weigh lithium hydroxide, three element hydroxides
Thing and nano titanium oxide are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcined mixed powder
Body, calcining heat are 900 DEG C, and soaking time is 10 hours, and 400 mesh sieves are crossed after natural cooling and obtain 50g 811 little particles, are put down
D50=2.0 μm.
According to chemical formula 0.80Li1.03Co0.94Ni0.03Al0.02Mn0.01O2·
0.20Li1.10Ni0.80Co0.10Mn0.09Ti0.01O2, weigh cobalt acid lithium monocrystalline bulky grain and the common 100g of 811 little particles, ball milling mixing 2
Hour, cobalt acid lithium and three element mixing materials are obtained, it is average D50=13.6 μm.
Embodiment 13
According to chemical formula Li1.10Co0.99B0.01O2Mol ratio weigh lithium carbonate, cobaltosic oxide and diboron trioxide and put
In ball grinder, the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcined mixed powder, calcining heat are 850 DEG C,
Soaking time is 10 hours, and 300 mesh sieves are crossed after natural cooling and obtain 100g cobalt acid lithium monocrystalline bulky grain, average D50=21.0 μ
m。
Li is calculated according to Horsfield models1.00Ni0.10Co0.80Mn0.10O2Short grained average D50 scopes are 0~
8.7 μm, design Li1.00Ni0.10Co0.80Mn0.10O2It is short grained average D50=8.7 μm.
According to chemical formula Li1.00Ni0.10Co0.80Mn0.10O2Mol ratio weigh lithium hydroxide and three element hydroxide are put
In ball grinder, the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcined mixed powder, calcining heat are 900 DEG C,
Soaking time is 4 hours, and 400 mesh sieves are crossed after natural cooling and obtain 50g 181 little particles.
According to chemical formula 0.67Li1.10Co0.99B0.01O2·0.33Li1.00Ni0.10Co0.80Mn0.10O2, weigh cobalt acid lithium list
Brilliant bulky grain and the common 100g of 181 little particles, ball milling mixing 2 hours, obtain cobalt acid lithium and three element mixing materials, average D50=
16.8μm。
Embodiment 14
According to chemical formula Li1.10Co0.99B0.01O2Mol ratio weigh lithium carbonate, cobaltosic oxide and diboron trioxide and put
In ball grinder, the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcined mixed powder, calcining heat are 850 DEG C,
Soaking time is 10 hours, and 300 mesh sieves are crossed after natural cooling and obtain 100g cobalt acid lithium monocrystalline bulky grain, average D50=21.0 μ
m。
Li is calculated according to Horsfield models1.00Ni0.10Co0.80Mn0.10O2Short grained average D50 scopes are 0~
8.7 μm, design Li1.00Ni0.10Co0.80Mn0.10O2It is short grained average D50=8.7 μm.
According to chemical formula Li1.00Ni0.10Co0.80Mn0.10O2Mol ratio weigh lithium hydroxide and three element hydroxide are put
In ball grinder, the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcined mixed powder, calcining heat are 900 DEG C,
Soaking time is 4 hours, and 400 mesh sieves are crossed after natural cooling and obtain 50g 181 little particles.
According to chemical formula 0.75Li1.10Co0.99B0.01O2·0.25Li1.00Ni0.10Co0.80Mn0.10O2, weigh cobalt acid lithium list
Brilliant bulky grain and the common 100g of 181 little particles, ball milling mixing 2 hours, obtain cobalt acid lithium and three element mixing materials, average D50=
17.9μm。
Embodiment 15
According to chemical formula Li1.10Co0.99B0.01O2Mol ratio weigh lithium carbonate, cobaltosic oxide and diboron trioxide and put
In ball grinder, the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcined mixed powder, calcining heat are 850 DEG C,
Soaking time is 10 hours, and 300 mesh sieves are crossed after natural cooling and obtain 100g cobalt acid lithium monocrystalline bulky grain, average D50=21.0 μ
m。
Li is calculated according to Horsfield models1.00Ni0.10Co0.80Mn0.10O2Short grained average D50 scopes are 0~
8.7 μm, design Li1.00Ni0.10Co0.80Mn0.10O2It is short grained average D50=8.7 μm.
According to chemical formula Li1.00Ni0.10Co0.80Mn0.10O2Mol ratio weigh lithium hydroxide and three element hydroxide are put
In ball grinder, the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcined mixed powder, calcining heat are 900 DEG C,
Soaking time is 4 hours, and 400 mesh sieves are crossed after natural cooling and obtain 50g 181 little particles.
According to chemical formula 0.80Li1.10Co0.99B0.01O2·0.20Li1.00Ni0.10Co0.80Mn0.10O2, weigh cobalt acid lithium list
Brilliant bulky grain and the common 100g of 181 little particles, ball milling mixing 2 hours, obtain cobalt acid lithium and three element mixing materials, average D50=
18.5μm。
Comparative example 1
According to chemical formula Li1.03Co0.99Ca0.005Nb0.005O2Mol ratio weigh lithium carbonate, cobaltosic oxide, nano oxygen
Change calcium and nanometer niobium pentaoxide is placed in ball grinder, the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcining is mixed
Powder is closed, calcining heat is 1020 DEG C, and soaking time is 4 hours, and 300 mesh sieves are crossed after natural cooling and obtain 100g cobalt acid lithium list
Brilliant bulky grain, it is average D50=15.0 μm.
Li is calculated according to Horsfield models1.05Ni0.79Mg0.01Co0.14Mo0.01Al0.05O2It is short grained average
D50 scopes are 0~6.2 μm, design Li1.05Ni0.79Mg0.01Co0.14Mo0.01Al0.05O2It is short grained average D50=2.0 μm.
According to chemical formula Li1.05Ni0.79Mg0.01Co0.14Mo0.01Al0.05O2Mol ratio weigh lithium hydroxide, three element hydrogens
Oxide, nano magnesia and metamolybdic acid ammonium are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.
Calcined mixed powder, calcining heat are 850 DEG C, and soaking time is 10 hours, and 400 mesh sieves are crossed after natural cooling and obtain 50g NCA
Little particle.
According to chemical formula 0.85Li1.03Co0.99Ca0.005Nb0.005O2·
0.15Li1.05Ni0.79Mg0.01Co0.14Mo0.01Al0.05O2, weigh cobalt acid lithium monocrystalline bulky grain and the common 100g of NCA little particles, ball milling
Mixing 2 hours, obtains cobalt acid lithium and three element mixing materials, average D50=12.9 μm.
Comparative example 2
According to chemical formula Li1.03Co0.99Ca0.005Nb0.005O2Mol ratio weigh lithium carbonate, cobaltosic oxide, nano oxygen
Change calcium and nanometer niobium pentaoxide is placed in ball grinder, the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcining is mixed
Powder is closed, calcining heat is 1020 DEG C, and soaking time is 4 hours, and 300 mesh sieves are crossed after natural cooling and obtain 100g cobalt acid lithium list
Brilliant bulky grain, it is average D50=15.0 μm.
Li is calculated according to Horsfield models1.05Ni0.79Mg0.01Co0.14Mo0.01Al0.05O2It is short grained average
D50 scopes are 0~6.2 μm, design Li1.05Ni0.79Mg0.01Co0.14Mo0.01Al0.05O2It is short grained average D50=2.0 μm.
According to chemical formula Li1.05Ni0.79Mg0.01Co0.14Mo0.01Al0.05O2Mol ratio weigh lithium hydroxide, three element hydrogens
Oxide, nano magnesia and metamolybdic acid ammonium are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.
Calcined mixed powder, calcining heat are 850 DEG C, and soaking time is 10 hours, and 400 mesh sieves are crossed after natural cooling and obtain 50g NCA
Little particle.
According to chemical formula 0.90Li1.03Co0.99Ca0.005Nb0.005O2·
0.10Li1.05Ni0.79Mg0.01Co0.14Mo0.01Al0.05O2, weigh cobalt acid lithium monocrystalline bulky grain and the common 100g of NCA little particles, ball milling
Mixing 2 hours, obtains cobalt acid lithium and three element mixing materials, average D50=13.6 μm.
Comparative example 3
According to chemical formula Li1.03Co0.99Ca0.005Nb0.005O2Mol ratio weigh lithium carbonate, cobaltosic oxide, nano oxygen
Change calcium and nanometer niobium pentaoxide is placed in ball grinder, the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.Calcining is mixed
Powder is closed, calcining heat is 1020 DEG C, and soaking time is 4 hours, and 300 mesh sieves are crossed after natural cooling and obtain 100g cobalt acid lithium list
Brilliant bulky grain, particle size range are average D50=15.0 μm.
Li is calculated according to Horsfield models1.05Ni0.79Mg0.01Co0.14Mo0.01Al0.05O2It is short grained average
D50 scopes are 0~6.2 μm, design Li1.05Ni0.79Mg0.01Co0.14Mo0.01Al0.05O2It is short grained average D50=2.0 μm.
According to chemical formula Li1.05Ni0.79Mg0.01Co0.14Mo0.01Al0.05O2Mol ratio weigh lithium hydroxide, three element hydrogens
Oxide, nano magnesia and metamolybdic acid ammonium are placed in ball grinder, and the mass ratio of ball material is 2:1, ball milling 6 hours, it is well mixed.
Calcined mixed powder, calcining heat are 850 DEG C, and soaking time is 10 hours, and 400 mesh sieves are crossed after natural cooling and obtain 50g NCA
Little particle.
According to chemical formula 0.95Li1.03Co0.99Ca0.005Nb0.005O2·
0.05Li1.05Ni0.79Mg0.01Co0.14Mo0.01Al0.05O2, weigh cobalt acid lithium monocrystalline bulky grain and the common 100g of NCA little particles, ball milling
Mixing 2 hours, obtains cobalt acid lithium and three element mixing materials, average D50=14.3 μm.
Evaluation method used for cobalt acid lithium and the compacted density of three element mixing materials of the invention is as follows：
The powder of the cobalt acid lithium and three element mixing materials is weighed into certain weight, is added in mould, on mould
Side applies 33MPa pressure, and pressurize 30 seconds, then the powder height in Measurement die, calculates the compacted density of powder.
Embodiment 1~15 and the cobalt acid lithium monocrystalline bulky grain of the preparation of comparative example 1~3, three element little particles, cobalt acid lithium and three
The powder compacted density of element mixing material, as shown in table 1.In embodiment and comparative example, the molecular formula of two kinds of positive electrodes and
Average D50 is changed, but due to the very close and different ternary of the molal weight between different cobalt acid lithium bulky grains
Molal weight between plain little particle is also very close to, therefore it is poor to ignore the mutual molal weight of cobalt acid lithium bulky grain
Influence of the different and molal weight difference that three element little particles are mutual to the powder compacted density of mixing material, only investigates two
Influences of the average D50 of kind positive electrode to the powder compacted density of mixing material.
Table 1
Three kinds of cobalt acid lithium monocrystalline in comparing embodiment (4,5,6), embodiment (10,11,12) and comparative example (1,2,3) are big
The compacted density of particle, it is known that the D50 increases of cobalt acid lithium monocrystalline bulky grain are advantageous to improve compacted density, when cobalt acid lithium monocrystalline is big
When the D50 of particle is higher than 16 μm, the compacted density can of independent cobalt acid lithium bulky grain reaches 4.40g/cm3More than.But if
The granularity of cobalt acid lithium monocrystalline bulky grain is excessive, and as shown in embodiment (13,14,15), its compacted density can be declined slightly on the contrary, this
Be because bulky grain between gap also increase, and due to play add gap effect the short grained particle diameter of three elements it is also corresponding
Increase, causes the gap between particle also to increase, it is impossible to reach highest compacted density.It is thus determined that big of cobalt acid lithium monocrystalline
The particle size range of grain is 16≤D50≤21 μm, according to the granularity of cobalt acid lithium monocrystalline bulky grain and Horsfield models (Niu Quanlin,
Zhang Minghui, Han Dong, Jia Tianyi.The analysis of mineral superfine powder filling effect, national high performance concrete seminar, 2002) calculate
It is 0 to go out the short grained particle size range of three elements<D50<9μm.The powder compacted density of three kinds of mixing materials of embodiment 4,5,6 is most
Height, all reach 4.50g/cm3More than, because the particle diameter of the mixing material of embodiment 4,5,6 and grading ratio are all close to most
The figure of merit.
Evaluation method used for cobalt acid lithium and the electrical property of three element mixing materials of the invention is as follows：
By the cobalt acid lithium and three element mixing materials with conductive carbon material and binding agent Vingon according to mass ratio
90:5:5 ratio is mixed, and 1-METHYLPYRROLIDONE is added dropwise and is ground to pasty state and is coated in aluminium foil surface, after 120 DEG C of drying
Positive pole test electrode is made.Experimental cell selects metal lithium sheet to electrode (reference electrode), and experimental cell selects CR2032 types
Battery component is assembled, and experimental cell, which is placed in insulating box and connects charge-discharge test instrument, carries out charge-discharge test.
Cobalt acid lithium and the field emission scanning electron microscope photo of three element mixing materials prepared by embodiment 4,5,6 is as schemed
Shown in 1, its 3.0~4.5V in half-cell passes through specific capacity-voltage curve such as Fig. 2 obtained by 0.1C/0.1C charge-discharge tests
Shown, the specific discharge capacity of these three mixing materials reaches more than 180mAh/g, and discharge platform is higher than 3.8V.Embodiment 4,5,6
The cobalt acid lithium material of preparation 3.0~4.6V in half-cell is bent by the specific capacity obtained by 0.1C/0.1C charge-discharge tests-voltage
Line, as shown in figure 3, the specific discharge capacity of these three mixing materials all reaches 204mAh/g, discharge platform is higher than 3.8V.
Cobalt acid lithium monocrystalline bulky grain, 523 little particles, cobalt acid lithium and three element mixing materials prepared by embodiment 4,5,6 exist
Such as scheme by specific capacity-cycle-index curve obtained by charge-discharge test under the conditions of 3.0~4.5V, 0.7C/0.7C in half-cell
Shown in 4, all cobalt acid lithiums and three element mixing materials all have preferable cycle performance, and after 50 weeks, it holds cycle charge-discharge
Conservation rate is measured more than 90%.Cobalt acid lithium monocrystalline bulky grain, 523 little particles, cobalt acid lithium and three elements prepared by embodiment 4,5,6
Mixing material is in half-cell by specific capacity-circulation time obtained by charge-discharge test under the conditions of 3.0~4.6V, 0.7C/0.7C
Number curve, as shown in figure 5, the cobalt acid lithium material that wherein prepared by embodiment 5 has best cycle performance, cycle charge-discharge 50 weeks
Afterwards, its capability retention is more than 85%.
Evaluation method used for cobalt acid lithium and the security performance of three element mixing materials of the invention is as follows：
The CR2032 type batteries assembled are placed in insulating box and connect charge-discharge test instrument and are charged, in 4.5V constant pressures
After stable, battery is removed.Take battery apart, take out the positive pole test electrode of Charging state, cleaned up with carbon dimethyl ester.Scrape just
Mixing material on pole test electrode, is put into platinum crucible, adds 1 drop electrolyte, then sealed crucible, is tested in heat analysis
Tested on instrument.
Cobalt acid lithium monocrystalline bulky grain, 523 little particles, cobalt acid lithium and three element mixing materials prepared by embodiment 4,5,6 exist
Thermal analysis curve in half-cell under 4.5V Charging states, as shown in fig. 6, the cobalt acid lithium of embodiment 4 and three element mixing materials
The exothermic temperature highest of exothermic peak, because cobalt acid lithium content therein is minimum, three constituent content is most, and the phase transformation of three elements is put
Hot temperature is higher than cobalt acid lithium.
Claims (10)
1. a kind of cobalt acid lithium and three element mixing materials, are made up of cobalt acid lithium monocrystalline bulky grain and three element little particles, its chemistry
Formula is (1-x) Li1+aCo1-bMbO2·xLi1+cNidCoeMnfM'gO2, wherein, Li1+aCo1-bMbO2Represent big of cobalt acid lithium monocrystalline
Grain, its particle size range are 16≤D50≤21 μm, 0≤a≤0.1,0<B≤0.1, M be Mg, Ca, Cu, Ni, B, Al, Cr, Fe, Ti,
One or more in Mn, Zr, V, Nb, Mo, W；Li1+cNidCoeMnfM'gO2Three element little particles are represented, its particle size range is 0<
D50<9 μm, 0≤c≤0.1,0.1≤d≤0.8,0.1≤e≤0.8,0≤f≤0.1,0≤g≤0.1, M' be Mg, Ca, Cu, B,
One or more in Al, Cr, Fe, Ti, Zr, V, Nb, Mo, W；Wherein x is that the short grained weight of three elements accounts for cobalt acid lithium and three
The percentage of the gross weight of element mixing material, 0<x≤0.5.
2. cobalt acid lithium as claimed in claim 1 and three element mixing materials, it is characterised in that the short grained grain of three elements
Footpath is calculated according to the particle diameter and Horsfield models of the cobalt acid lithium bulky grain.
3. cobalt acid lithium as claimed in claim 1 and three element mixing materials, it is characterised in that the cobalt acid lithium and three elements mix
The particle size range of condensation material is 10≤D50≤20 μm.
4. the preparation method of any described cobalt acid lithiums of claim 1-3 and three element mixing materials, passes through a solid phase mixing
Sintering is realized, is comprised the following steps：
1-1) the molar ratio weighing lithium source of element shown in the chemical formula by cobalt acid lithium and three element mixing materials, cobalt precursor,
The auxiliary material of three elemental precursors, the auxiliary material containing M element and the element containing M', solid phase mixing are uniform；
1-2) by step 1-1) in obtained mixed powder in 700~1100 DEG C of calcinings, soaking time is 2~10 hours, natural
Sieving obtains cobalt acid lithium and three element mixing materials after cooling.
5. preparation method as claimed in claim 4, it is characterised in that step 1-1) described in lithium source be lithium carbonate and hydroxide
The mixture of one or both of lithium, the cobalt precursor are cobaltosic oxide, hydroxy cobalt oxide, cobalt hydroxide and cobalt carbonate
In one or more mixtures, three elemental precursor is oxide, oxyhydroxide, the hydrogen of the element containing Ni/Co/Mn
One or more mixtures in oxide and carbonate, the auxiliary material containing M element are M oxides, hydroxide, second
One or more mixtures in hydrochlorate, carbonate, subcarbonate, the auxiliary material of the element containing M' is M oxide, hydrogen
One or more mixtures in oxide, acetate, carbonate, subcarbonate.
6. the preparation method of any described cobalt acid lithiums of claim 1-3 and three element mixing materials, passes through solid phase mixing twice
Sintering is realized, is comprised the following steps：
2-1) the molar ratio weighing cobalt precursor of element shown in the chemical formula by cobalt acid lithium and the auxiliary material containing M element, solid phase are mixed
Close uniform；
2-2) elemental precursor of molar ratio weighing three of element and the auxiliary material of the element containing M' shown in the chemical formula by three elements, Gu
Mix uniformly；
2-3) weigh lithium source, step 2-1 by the chemical formula of cobalt acid lithium and three element mixing materials) in obtained body containing cobalt powder and step
Rapid 2-2) in obtain contain three element powders, solid phase mixing is uniform, then 700~1100 DEG C calcining, soaking time be 2~10
Hour, sieved after natural cooling and obtain cobalt acid lithium and three element mixing materials.
7. preparation method as claimed in claim 6, it is characterised in that step 2-1) described in cobalt precursor be four oxidations three
One or more mixtures in cobalt, hydroxy cobalt oxide, cobalt hydroxide and cobalt carbonate, the auxiliary material containing M element are M oxygen
One or more mixtures in compound, hydroxide, acetate, carbonate, subcarbonate；Step 2-2) described in three
Elemental precursor is the one or more in oxide, oxyhydroxide, hydroxide and the carbonate of the element containing Ni/Co/Mn
Mixture, the auxiliary material of the element containing M' is in M' oxide, hydroxide, acetate, carbonate, subcarbonate
One or more mixtures；Step 2-3) described in lithium source be one or both of lithium carbonate and lithium hydroxide mixing
Thing.
8. the preparation method of any described cobalt acid lithiums of claim 1-3 and three element mixing materials, by sintering solid phase respectively
Mixing is realized, is comprised the following steps：
3-1) molar ratio weighing lithium source, cobalt precursor and the auxiliary material containing M element of element shown in the chemical formula by cobalt acid lithium, Gu
Mix uniformly, be then 2~10 hours in 850~1100 DEG C of calcinings, soaking time, being sieved after natural cooling obtains cobalt acid lithium
Monocrystalline bulky grain；
3-2) the molar ratio weighing lithium source of element shown in the chemical formula by three elements, three elemental precursors and the element containing M' is auxiliary
Material, solid phase mixing is uniform, is then 2~10 hours in 700~1100 DEG C of calcinings, soaking time, being sieved after natural cooling obtains
Three element little particles；
3-3) weighed by the chemical formula of cobalt acid lithium and three element mixing materials by step 3-1) in obtained big of cobalt acid lithium monocrystalline
Grain and step 3-2) in obtained three element little particles, solid phase mixing is uniform, obtains cobalt acid lithium and three element mixing materials.
9. preparation method as claimed in claim 8, it is characterised in that step 3-1) described in lithium source be lithium carbonate and hydroxide
The mixture of one or both of lithium, the cobalt precursor are cobaltosic oxide, hydroxy cobalt oxide, cobalt hydroxide and cobalt carbonate
In one or more mixtures, the auxiliary material containing M element is M oxide, hydroxide, acetate, carbonate, alkali
One or more mixtures in formula carbonate；Step 3-2) described in lithium source be one kind in lithium carbonate, lithium hydroxide or
Two kinds of mixture, three elemental precursor are oxide, oxyhydroxide, hydroxide and the carbon of the element containing Ni/Co/Mn
One or more mixtures in hydrochlorate, the auxiliary material of the element containing M' is M' oxide, hydroxide, acetate, carbon
One or more mixtures in hydrochlorate, subcarbonate.
10. preparation method as claimed in claim 8, it is characterised in that step 3-1) described in cobalt acid lithium monocrystalline bulky grain
Particle size range is 18≤D50≤21 μm, step 3-2) described in the short grained particle size range of three elements be 1≤D50≤5 μm.
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| WO2019211366A1 (en) * | 2018-05-04 | 2019-11-07 | Umicore | A lithium cobalt oxide secondary battery comprising a fluorinated electrolyte and a positive electrode material for high voltage applications |
| CN110474085A (en) * | 2019-08-12 | 2019-11-19 | 深圳市科瑞隆科技有限公司 | High temperature modification high-voltage lithium ion batteries and preparation method thereof |
| CN112151791A (en) * | 2020-09-08 | 2020-12-29 | 北大先行泰安科技产业有限公司 | Lithium-balanced lithium cobaltate mixed material and preparation and detection methods thereof |
| CN115000369A (en) * | 2022-05-31 | 2022-09-02 | 上海瑞浦青创新能源有限公司 | Positive electrode material, positive electrode plate and lithium ion battery |
| US11916224B2 (en) | 2018-03-02 | 2024-02-27 | Umicore | Positive electrode material for rechargeable lithium ion batteries |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101369658A (en) * | 2007-08-13 | 2009-02-18 | 深圳市比克电池有限公司 | Anode active material, positive plate of lithium ion battery and lithium ion battery |
| CN101405899A (en) * | 2006-03-20 | 2009-04-08 | 株式会社Lg化学 | Cathode materials for lithium battery having higher performance |
| CN101901906A (en) * | 2010-07-22 | 2010-12-01 | 东莞新能源科技有限公司 | Lithium ion secondary battery and cathode material prepared by same |
| CN101901907A (en) * | 2010-07-22 | 2010-12-01 | 东莞新能源科技有限公司 | Lithium ion secondary battery and cathode material prepared by same |
| CN102017245A (en) * | 2008-04-24 | 2011-04-13 | 波士顿电力公司 | Lithium-ion secondary battery |
| CN102569722A (en) * | 2012-02-20 | 2012-07-11 | 宁德新能源科技有限公司 | Lithium ion secondary battery and anode thereof |
| CN102751485A (en) * | 2012-07-17 | 2012-10-24 | 中国电子科技集团公司第十八研究所 | Preparation method of composite cathode material for lithium ion battery |
| 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 |
| CN103570082A (en) * | 2012-08-01 | 2014-02-12 | 北京当升材料科技股份有限公司 | Preparation method of lithium cobaltate |
| 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 |
-
2017
- 2017-06-15 CN CN201710450488.1A patent/CN107482211A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101405899A (en) * | 2006-03-20 | 2009-04-08 | 株式会社Lg化学 | Cathode materials for lithium battery having higher performance |
| CN101369658A (en) * | 2007-08-13 | 2009-02-18 | 深圳市比克电池有限公司 | Anode active material, positive plate of lithium ion battery and lithium ion battery |
| CN102017245A (en) * | 2008-04-24 | 2011-04-13 | 波士顿电力公司 | Lithium-ion secondary battery |
| CN101901906A (en) * | 2010-07-22 | 2010-12-01 | 东莞新能源科技有限公司 | Lithium ion secondary battery and cathode material prepared by same |
| CN101901907A (en) * | 2010-07-22 | 2010-12-01 | 东莞新能源科技有限公司 | Lithium ion secondary battery and cathode material prepared by same |
| 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 |
| CN102569722A (en) * | 2012-02-20 | 2012-07-11 | 宁德新能源科技有限公司 | Lithium ion secondary battery and anode thereof |
| CN102751485A (en) * | 2012-07-17 | 2012-10-24 | 中国电子科技集团公司第十八研究所 | Preparation method of composite cathode material for lithium ion battery |
| CN103570082A (en) * | 2012-08-01 | 2014-02-12 | 北京当升材料科技股份有限公司 | Preparation method of lithium cobaltate |
| 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 |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11916224B2 (en) | 2018-03-02 | 2024-02-27 | Umicore | Positive electrode material for rechargeable lithium ion batteries |
| US11949096B2 (en) | 2018-03-02 | 2024-04-02 | Umicore | Positive electrode material for rechargeable lithium ion batteries |
| WO2019211366A1 (en) * | 2018-05-04 | 2019-11-07 | Umicore | A lithium cobalt oxide secondary battery comprising a fluorinated electrolyte and a positive electrode material for high voltage applications |
| CN109786732A (en) * | 2018-12-28 | 2019-05-21 | 广东邦普循环科技有限公司 | Multimodal powder based on lithium transition-metal oxide and the application in rechargeable battery |
| CN110474085A (en) * | 2019-08-12 | 2019-11-19 | 深圳市科瑞隆科技有限公司 | High temperature modification high-voltage lithium ion batteries and preparation method thereof |
| CN112151791A (en) * | 2020-09-08 | 2020-12-29 | 北大先行泰安科技产业有限公司 | Lithium-balanced lithium cobaltate mixed material and preparation and detection methods thereof |
| CN112151791B (en) * | 2020-09-08 | 2022-04-01 | 泰丰先行(泰安)科技有限公司 | Lithium-balanced lithium cobaltate mixed material and preparation and detection methods thereof |
| CN115000369A (en) * | 2022-05-31 | 2022-09-02 | 上海瑞浦青创新能源有限公司 | Positive electrode material, positive electrode plate and lithium ion battery |
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