CN114261997A - Nickel-cobalt hydroxide and preparation method thereof, nickel-cobalt oxide, lithium ion battery positive electrode material, positive electrode, battery and electric equipment - Google Patents
Nickel-cobalt hydroxide and preparation method thereof, nickel-cobalt oxide, lithium ion battery positive electrode material, positive electrode, battery and electric equipment Download PDFInfo
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- CN114261997A CN114261997A CN202111623523.8A CN202111623523A CN114261997A CN 114261997 A CN114261997 A CN 114261997A CN 202111623523 A CN202111623523 A CN 202111623523A CN 114261997 A CN114261997 A CN 114261997A
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- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 title claims abstract description 120
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 133
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 105
- 239000013078 crystal Substances 0.000 claims abstract description 78
- 238000000975 co-precipitation Methods 0.000 claims abstract description 56
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 45
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 45
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000007788 liquid Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 36
- 239000003513 alkali Substances 0.000 claims description 32
- 238000005406 washing Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 25
- 238000010304 firing Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 38
- 235000011121 sodium hydroxide Nutrition 0.000 description 28
- 239000000243 solution Substances 0.000 description 24
- 239000002184 metal Substances 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000635 electron micrograph Methods 0.000 description 12
- 239000002243 precursor Substances 0.000 description 10
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 9
- 229940044175 cobalt sulfate Drugs 0.000 description 9
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 9
- 239000012266 salt solution Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000004154 testing of material Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a nickel-cobalt hydroxide, a preparation method, a nickel-cobalt oxide, a lithium ion battery positive electrode material, a positive electrode, a battery and an electric device. The nickel-cobalt hydroxide comprises an inner core area, a middle area and an outer shell area, wherein the middle area covers the inner core area, and the outer shell area covers the middle area; the porosity of the intermediate zone is greater than the porosity of the core zone and the porosity of the shell zone. The preparation method of the nickel cobalt hydroxide comprises the following steps: mixing raw materials including a nickel-cobalt binary aqueous solution, a sodium hydroxide aqueous solution and ammonia water, and obtaining seed crystals through a first coprecipitation reaction; and mixing the raw materials including the seed crystal, the nickel-cobalt binary aqueous solution, the sodium hydroxide aqueous solution and ammonia water, and carrying out a second coprecipitation reaction to obtain the nickel-cobalt hydroxide. The nickel cobalt hydroxide provided by the application has special pore distribution and stable material structure, and can effectively improve the capacity, the cycle performance, the safety and the like of the battery.
Description
Technical Field
The application relates to the field of lithium ion batteries, in particular to a nickel-cobalt hydroxide, a preparation method, a nickel-cobalt oxide, a lithium ion battery anode material, an anode, a battery and an electric device.
Background
The automobile industry in the world is rapidly developing, and lithium batteries are increasingly applied to the automobile industry as a new environment-friendly power energy source. The anode precursor material is the most important component of the lithium battery and is always the core of the technology. At present, the most common 5-series and 6-series ternary precursors exist in the market, but the capacitance is low, so that the application of the ternary precursors in new energy automobiles is limited.
Some precursor manufacturers have already developed 8-series and 9-series high-nickel large-particle ternary and binary precursors in order to compete for market resources, but the problems of poor cycle performance, poor safety and the like of the 8-series and 9-series high-nickel large-particle ternary and binary precursors are not solved all the time, and cannot be popularized comprehensively.
The precursor with high nickel and large particles is generally synthesized by a batch method, has extremely narrow particle size distribution, and can also ensure that the particle structure has strong uniformity. The battery prepared from the loose precursor has high capacity and good rate performance, but the particle strength is insufficient, the particles are easy to break in multiple charging and discharging processes, the electric capacity is influenced, the cycle performance is poor, and safety accidents are easy to happen. The battery prepared by the compact precursor has large lithium ion diffusion resistance and insufficient rate capability.
Therefore, how to improve the cycle performance, safety and the like of the ternary and binary precursors with 8-series and 9-series high-nickel large particles is a major difficulty faced at present.
Disclosure of Invention
The application aims to provide a nickel-cobalt hydroxide, a preparation method thereof, a nickel-cobalt oxide, a lithium ion battery positive electrode material, a positive electrode, a battery and an electric device, so as to solve the problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a nickel cobalt hydroxide comprising an inner core region, an intermediate region, and an outer shell region, the intermediate region encasing the inner core region and the outer shell region encasing the intermediate region;
the porosity of the intermediate region is greater than the porosity of the inner core region and the porosity of the shell region.
Preferably, the nickel cobalt hydroxide satisfies at least one of the following conditions:
a. the porosity of the intermediate zone is 5% -10%, and the porosity of the inner core zone and the porosity of the outer shell zone are respectively and independently 1% -5%;
b. the pores of the inner core area are distributed in a network shape, the pores of the middle area are radially dispersed to the shell area, and the pores of the shell area are distributed in a scattered point shape;
c. the diameter of the inner core area is 3-6 μm;
d. the diameter of the middle area is 5-14 μm;
e. the diameter of the shell area is 10-16 μm;
f. the peak intensity ratio (I101: I001) of the nickel cobalt hydroxide is not less than 1.1;
g. the nickel cobalt hydroxide has a peak intensity ratio (I101: I001) of 1.2 to 1.5;
h. the 001 half-peak width of the nickel-cobalt hydroxide is 0.5-0.9, and the 101 half-peak width is 0.45-0.85;
i. the nickel cobalt hydroxide has (D95-D5)/D50 of 0.35-0.5.
Preferably, the nickel cobalt hydroxide has the formula of NixCo(1-x)(OH)2Wherein x is more than or equal to 0.8<1.0。
The application also provides a preparation method of the nickel cobalt hydroxide, which comprises the following steps:
mixing raw materials including a nickel-cobalt binary aqueous solution, a sodium hydroxide aqueous solution and ammonia water, and obtaining seed crystals through a first coprecipitation reaction;
and mixing the raw materials including the seed crystal, the nickel-cobalt binary aqueous solution, the sodium hydroxide aqueous solution and ammonia water, and carrying out a second coprecipitation reaction to obtain the nickel-cobalt hydroxide.
Preferably, the preparation method satisfies at least one of the following conditions:
j. the concentration of the nickel-cobalt binary aqueous solution is 80g/L-120 g/L;
k. in the processes of the first coprecipitation reaction and the second coprecipitation reaction, the flow rates of the nickel-cobalt binary aqueous solution and the aqueous solution of the sodium hydroxide are respectively 300L/h-600L/h independently, the flow rates of the aqueous solution of the sodium hydroxide are respectively 60L/h-250L/h independently, and the flow rates of the aqueous solution of the ammonia are respectively 10L/h-50L/h independently;
in the processes of the first coprecipitation reaction and the second coprecipitation reaction, the temperature is 40-60 ℃ respectively and the stirring speed is 180-220 r/min respectively;
m. during the first coprecipitation reaction, the pH is between 10 and 13; in the process of the second coprecipitation reaction, the pH control range of the system is as follows: the pH value is 10.3-10.8 within 2 days after the reaction, and the pH value is 11.4-12 after the reaction is carried out for 3 days until the reaction is finished;
n, the grain size of the seed crystal is 3-7 μm;
o. after the first coprecipitation reaction is finished, obtaining the seed crystal with the moisture content of less than or equal to 25% through solid-liquid separation;
p. the particle size of the nickel cobalt hydroxide is not less than 12 μm;
q. after the second co-precipitation reaction further comprising: sequentially carrying out alkali washing, water washing, solid-liquid separation and drying on a reaction product;
the concentration of the sodium hydroxide aqueous solution used for alkaline washing is 3-10 wt%; the drying temperature is 90-150 ℃.
The application also provides a nickel cobalt oxide, wherein the nickel cobalt oxide comprises a first region, a second region and a third region, the second region coats the first region, and the third region coats the second region;
the porosity of the second region is greater than the porosity of the first region, and the porosity of the second region is greater than or equal to the porosity of the third region.
Preferably, the nickel cobalt oxide satisfies at least one of the following conditions:
r. the porosity of the first region is 3% to 10%, the porosity of the second region is 15% to 25%, and the porosity of the third region is 5% to 15%;
s. the diameter of the first region is from 3 μm to 6 μm, the diameter of the second region is from 5 μm to 14 μm, and the diameter of the third region is from 10 μm to 16 μm;
t. the nickel cobalt oxide has (D95-D5)/D50 of 0.18-0.32;
u. the nickel cobalt oxide has a peak intensity ratio (I012: I101) of not less than 1.4, a 101 half-peak width of 0.50-0.85, and a 012 half-peak width of 0.60-0.95;
v. the molecular formula of the nickel cobalt oxide is NiyCo(1-y)O, wherein y is more than or equal to 0.8<1.0。
Preferably, the nickel cobalt oxide is obtained by firing a nickel cobalt hydroxide, wherein the nickel cobalt hydroxide comprises an inner core region, a middle region and an outer shell region, the middle region covers the inner core region, and the outer shell region covers the middle region; the porosity of the intermediate region is greater than the porosity of the inner core region and the porosity of the shell region;
preferably, the firing satisfies at least one of the following conditions:
the firing temperature is 400-600 ℃;
x, in the firing process, the feeding amount of the kiln is 200kg/h-500kg/h, the air inlet and outlet quantity of the kiln is 400m3/h-600m3The rotation speed of the kiln is 1r/min-6 r/min.
The application also provides a lithium ion battery cathode material, the raw material of which comprises the nickel cobalt hydroxide or the nickel cobalt oxide.
The application also provides a lithium ion battery anode, and the raw material of the lithium ion battery anode comprises the lithium ion battery anode material.
The application also provides a lithium ion battery, which comprises the lithium ion battery anode.
The application also provides an electric device, which comprises the lithium ion battery or is powered by the lithium ion battery.
Compared with the prior art, the beneficial effect of this application includes:
the nickel-cobalt hydroxide provided by the application has an inner core area, a middle area and an outer shell area, and the porosity of the middle area is greater than that of the inner core area and that of the outer shell area; the porosity of the core area is low, so that the material structure can be stabilized, and the stability of a battery product is ensured; the porosity of the middle area is high, the lithium diffusion resistance is reduced, the discharge capacity is increased, and the charge-discharge efficiency is improved; the shell area has low porosity and high structural strength, prevents the battery from particle breakage under continuous charging and discharging, and improves the battery capacity, the cycle performance, the safety and other performances.
According to the preparation method of the nickel-cobalt hydroxide, the obtained nickel-cobalt hydroxide has special pore distribution, and the stability of the material and the performance of the battery can be effectively improved.
The nickel-cobalt oxide provided by the present application is obtained by firing the above nickel-cobalt hydroxide, and has a first region, a second region, and a third region similar to the above nickel-cobalt hydroxide, and the porosity of the second region is greater than the porosity of the first region, and the porosity of the second region is greater than or equal to the porosity of the third region, and an effect similar to the above nickel-cobalt hydroxide can be obtained.
The lithium ion battery anode material, the anode, the battery and the electric equipment have the advantages of good stability, high electrical property and good safety.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a schematic diagram of the structure of a nickel cobalt hydroxide provided herein;
FIG. 2 is a plot of the multiple narrow peak analytical particle size distribution of the nickel cobalt hydroxide obtained in example 1;
FIG. 3 is a multi-narrow-peak analytical particle size distribution diagram of the nickel cobalt oxide obtained in example 1;
FIG. 4 is an XRD pattern of nickel cobalt hydroxide obtained in example 1;
FIG. 5 is an XRD pattern of nickel cobalt oxide obtained in example 1;
FIG. 6 is a surface electron micrograph of a nickel cobalt hydroxide obtained in example 1;
FIG. 7 is a sectional electron micrograph of a nickel cobalt hydroxide obtained in example 1;
FIG. 8 is a surface electron micrograph of a nickel cobalt oxide obtained in example 1;
FIG. 9 is a sectional electron micrograph of a nickel cobalt oxide obtained in example 1;
FIG. 10 is a high power electron micrograph of a nickel cobalt oxide obtained in example 1;
FIG. 11 is a sectional electron micrograph of a nickel cobalt hydroxide obtained in comparative examples 1 to 4.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A nickel cobalt hydroxide comprising an inner core region, an intermediate region, and an outer shell region, the intermediate region encasing the inner core region and the outer shell region encasing the intermediate region;
the porosity of the intermediate region is greater than the porosity of the inner core region and the porosity of the shell region.
In an alternative embodiment, the nickel cobalt hydroxide satisfies at least one of the following conditions:
a. the porosity of the intermediate zone is 5% -10%, and the porosity of the inner core zone and the porosity of the outer shell zone are respectively and independently 1% -5%;
optionally, the porosity of the intermediate region may be any value between 5%, 6%, 7%, 8%, 9%, 10%, or 5% to 10%, and the porosity of the inner core region and the porosity of the outer shell region may each independently be any value between 1%, 2%, 3%, 4%, 5%, or 1% to 5%;
b. the pores of the inner core area are distributed in a network shape, the pores of the middle area are radially dispersed to the shell area, and the pores of the shell area are distributed in a scattered point shape;
c. the diameter of the inner core area is 3-6 μm;
d. the diameter of the middle area is 5-14 μm;
e. the diameter of the shell area is 10-16 μm;
fig. 1 is a schematic structural diagram of a nickel cobalt hydroxide provided herein. As shown in FIG. 1, region A corresponds to the core region, region B corresponds to the intermediate region, and region C corresponds to the shell region.
It should be noted that the diameter referred to herein refers to the distance from one edge of the region to the other edge through the center of the circle, for example, the diameter of the shell region refers to the diameter of the entire nickel cobalt hydroxide particle, not the thickness of the region.
Alternatively, the diameter of the inner core region may be 3 μm, 4 μm, 5 μm, 6 μm or any value between 3 μm and 6 μm; the diameter of the intermediate region may be any value between 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 5 μm-14 μm; the diameter of the shell region may be any value between 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm or 10 μm-16 μm;
f. the peak intensity ratio (I101: I001) of the nickel cobalt hydroxide is not less than 1.1;
g. the nickel cobalt hydroxide has a peak intensity ratio (I101: I001) of 1.2 to 1.5;
h. the 001 half-peak width of the nickel-cobalt hydroxide is 0.5-0.9, and the 101 half-peak width is 0.45-0.85;
i. the nickel cobalt hydroxide has (D95-D5)/D50 of 0.35-0.5.
The peak intensity ratio in the XRD pattern of the product is high, and the particles in the product are arranged orderly under the peak intensity ratio and the half peak width, so that the cycle performance of the battery can be improved.
Optionally, the nickel cobalt hydroxide may have a peak intensity ratio (I101: I001) of 1.2, 1.3, 1.4, 1.5, or any value between 1.2 and 1.5; the half-width at 001 of the nickel cobalt hydroxide can be any value between 0.5, 0.6, 0.7, 0.8, 0.9 or 0.5 and 0.9, and the half-width at 101 can be any value between 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85 or 0.45 and 0.85; the nickel cobalt hydroxide may have (D95-D5)/D50 of any value between 0.35, 0.40, 0.45, 0.5, or 0.35-0.5.
In an alternative embodiment, the nickel cobalt hydroxide has the formula NixCo(1-x)(OH)2Wherein x is more than or equal to 0.8<1.0。
The application also provides a preparation method of the nickel cobalt hydroxide, which comprises the following steps:
mixing raw materials including a nickel-cobalt binary aqueous solution, a sodium hydroxide aqueous solution and ammonia water, and obtaining seed crystals through a first coprecipitation reaction;
and mixing the raw materials including the seed crystal, the nickel-cobalt binary aqueous solution, the sodium hydroxide aqueous solution and ammonia water, and carrying out a second coprecipitation reaction to obtain the nickel-cobalt hydroxide.
In an alternative embodiment, the preparation method satisfies at least one of the following conditions:
j. the concentration of the nickel-cobalt binary aqueous solution is 80g/L-120 g/L;
optionally, the concentration of the nickel-cobalt binary aqueous solution can be any value between 80g/L, 90g/L, 100g/L, 110g/L, 120g/L or 80g/L-120 g/L;
k. in the processes of the first coprecipitation reaction and the second coprecipitation reaction, the flow rates of the nickel-cobalt binary aqueous solution and the aqueous solution of the sodium hydroxide are respectively 300L/h-600L/h independently, the flow rates of the aqueous solution of the sodium hydroxide are respectively 60L/h-250L/h independently, and the flow rates of the aqueous solution of the ammonia are respectively 10L/h-50L/h independently;
optionally, in the processes of the first coprecipitation reaction and the second coprecipitation reaction, the flow rates of the nickel-cobalt binary aqueous solution may be, independently of each other, any value between 300L/h, 400L/h, 500L/h, 600L/h, or 300L/h and 600L/h, and the flow rates of the sodium hydroxide aqueous solution may be, independently of each other, any value between 60L/h, 70L/h, 80L/h, 90L/h, 100L/h, 110L/h, 120L/h, 130L/h, 140L/h, 150L/h, 160L/h, 170L/h, 180L/h, 190L/h, 200L/h, 210L/h, 220L/h, 230L/h, 240L/h, 250L/h, or 60L/h and 250L/h, the flow rate of the ammonia water can be any value of 10L/h, 20L/h, 30L/h, 40L/h, 50L/h or 10L/h-50L/h independently;
in the processes of the first coprecipitation reaction and the second coprecipitation reaction, the temperature is 40-60 ℃ respectively and the stirring speed is 180-220 r/min respectively;
optionally, in the processes of the first coprecipitation reaction and the second coprecipitation reaction, the temperature may be any value between 40 ℃, 50 ℃, 60 ℃ or 40 ℃ to 60 ℃ respectively and independently, and the stirring speed may be any value between 180r/min, 190r/min, 200r/min, 210r/min, 220r/min or 180r/min to 220r/min respectively and independently;
m. during the first coprecipitation reaction, the pH is between 10 and 13; in the process of the second coprecipitation reaction, the pH control range of the system is as follows: the pH value is 10.3-10.8 within 2 days after the reaction, and the pH value is 11.4-12 after the reaction is carried out for 3 days until the reaction is finished;
optionally, during the first co-precipitation reaction, the pH may be any value between 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9, 11, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12, 12.1, 12.2, 12.3, 12.4, 12.5, 12.6, 12.7, 12.8, 12.9, 13, or 10-13; in the process of the second coprecipitation reaction, the pH control range of the system is as follows: the pH value within 2 days of the reaction can be any value between 10.3, 10.4, 10.5, 10.6, 10.7, 10.8 or 10.3 and 10.8, and the pH value from 3 days of the reaction to the end of the reaction can be any value between 11.4, 11.5, 11.6, 11.7, 11.8, 11.9, 12 or 11.4 and 12;
n, the grain size of the seed crystal is 3-7 μm;
optionally, the grain size of the seed crystal can be 3 μm, 4 μm, 5 μm, 6 μm, 7 μm or any value between 3 μm and 7 μm;
o. after the first coprecipitation reaction is finished, obtaining the seed crystal with the moisture content of less than or equal to 25% through solid-liquid separation;
p. the particle size of the nickel cobalt hydroxide is not less than 12 μm;
q. after the second co-precipitation reaction further comprising: sequentially carrying out alkali washing, water washing, solid-liquid separation and drying on a reaction product;
the concentration of the sodium hydroxide aqueous solution used for alkaline washing is 3-10 wt%; the drying temperature is 90-150 ℃.
Alternatively, the concentration of the aqueous sodium hydroxide solution used for the alkaline washing may be 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, or any value between 3 wt% and 10 wt%; the drying temperature can be any value between 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 90 ℃ to 150 ℃.
The application also provides a nickel cobalt oxide, wherein the nickel cobalt oxide comprises a first region, a second region and a third region, the second region coats the first region, and the third region coats the second region;
the porosity of the second region is greater than the porosity of the first region, and the porosity of the second region is greater than or equal to the porosity of the third region.
In an alternative embodiment, the nickel cobalt oxide satisfies at least one of the following conditions:
r. the porosity of the first region is 3% to 10%, the porosity of the second region is 15% to 25%, and the porosity of the third region is 5% to 15%;
alternatively, the porosity of the first region may be any value between 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or 3% and 10%, the porosity of the second region may be any value between 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, or 15% and 25%, and the porosity of the third region may be any value between 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, or 5% and 15%;
s. the diameter of the first region is from 3 μm to 6 μm, the diameter of the second region is from 5 μm to 14 μm, and the diameter of the third region is from 10 μm to 16 μm;
alternatively, the diameter of the first region may be 3 μm, 4 μm, 5 μm, 6 μm or any value between 3 μm and 6 μm, the diameter of the second region may be 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or any value between 5 μm and 14 μm, and the diameter of the third region may be 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm or any value between 10 μm and 16 μm;
t. the nickel cobalt oxide has (D95-D5)/D50 of 0.18-0.32;
u. the nickel cobalt oxide has a peak intensity ratio (I012: I101) of not less than 1.4, a 101 half-peak width of 0.50-0.85, and a 012 half-peak width of 0.60-0.95;
optionally, (D95-D5)/D50 of the nickel cobalt oxide may be any value between 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.30, 0.31, 0.32 or 0.18-0.32; the half-width at half-maximum of 101 may be any value between 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85 or 0.50-0.85, and the half-width at half-maximum of 012 may be any value between 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95 or 0.60-0.95;
v. the molecular formula of the nickel-cobalt oxide is NiyCo(1-y)O, wherein y is more than or equal to 0.8<1.0。
In an alternative embodiment, the nickel cobalt oxide is fired using a nickel cobalt hydroxide, the nickel cobalt hydroxide comprising an inner core region, an intermediate region, and an outer shell region, the intermediate region encasing the inner core region, and the outer shell region encasing the intermediate region; the porosity of the intermediate region is greater than the porosity of the inner core region and the porosity of the shell region;
in an alternative embodiment, the firing satisfies at least one of the following conditions:
the firing temperature is 400-600 ℃;
x, in the firing process, the feeding amount of the kiln is 200kg/h-500kg/h, and the air inlet and outlet amount of the kiln is 400m3/h-600m3The rotation speed of the kiln is 1r/min-6 r/min.
Firing is a process of sintering and oxidizing a hydroxide to an oxide in a predetermined gas atmosphere at an appropriate temperature and for an appropriate time to give a specific structure. The gas atmosphere is controlled by the air inlet and outlet quantity of the kiln. The sintering effect can be influenced by the temperature and the time in the sintering process, the temperature is too low, the time is too short, the material is not oxidized sufficiently, the temperature is too high, the time is too long, the material is oxidized excessively, the structure is damaged, and the sintering time in the kiln is controlled by the rotating speed of the kiln.
Optionally, the firing temperature may be any value between 400 ℃, 500 ℃, 600 ℃ or 400 ℃ to 600 ℃; in the firing process, the feeding amount of the kiln can be any value of 200kg/h, 250kg/h, 300kg/h, 350kg/h, 400kg/h, 450kg/h, 500kg/h or 200kg/h-500kg/h, and the air inlet and outlet amount of the kiln can be 400m3/h、500m3/h、600m3H or 400m3/h-600m3The rotating speed of the kiln can be any value between 1r/min, 1.5r/min, 2r/min, 2.5r/min, 3r/min, 3.5r/min, 4r/min, 4.5r/min, 5r/min, 5.5r/min, 6r/min or any value between 1r/min and 6 r/min.
The application also provides a lithium ion battery cathode material, the raw material of which comprises the nickel cobalt hydroxide or the nickel cobalt oxide.
The application also provides a lithium ion battery anode, and the raw material of the lithium ion battery anode comprises the lithium ion battery anode material.
The application also provides a lithium ion battery, which comprises the lithium ion battery anode.
The application also provides an electric device, which comprises the lithium ion battery or is powered by the lithium ion battery.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
(1) Dissolving a certain amount of nickel sulfate crystals and cobalt sulfate crystals in water, and mixing to prepare a mixed metal salt solution with the nickel-cobalt ratio of 92:8 and the metal concentration of 110 g/L.
(2) Adding 8m into a reaction kettle3Adjusting the pH value of water and a proper amount of liquid caustic soda and ammonia water to 12.0, starting reaction at a rotating speed of 200r/min, wherein the flow rate of the binary solution is 400L/h, the flow rate of the liquid caustic soda is 200L/h, the flow rate of the ammonia water is 30L/h, and carrying out coprecipitation reaction under the condition of keeping the reaction temperature at 60 ℃ to obtain the crystal seeds with the particle size of 5.0 microns.
(3) And (4) dehydrating and spin-drying the seed crystal by using a centrifugal machine to obtain the seed crystal wet material with the water content of about 20%.
(4) Adopting a batch method for reaction, putting 150kg of seed crystal into a reaction kettle added with liquid alkali and ammonia water, starting the reaction at the rotating speed of 200r/min, wherein the flow rate of the binary solution is 500L/h, the flow rate of the liquid alkali is 200L/h, the flow rate of the ammonia water is 30L/h, keeping the conditions of the reaction temperature of 50 ℃ and the pH value of 10.5, carrying out coprecipitation reaction, enabling the seed crystal to slowly grow, and adjusting the pH value to 11.4 at the later stage (3d-5d) to prepare the nickel-cobalt hydroxide with the particle size of 16 mu m.
(5) And respectively carrying out alkaline washing and water washing on the nickel-cobalt hydroxide slurry by using 10% diluted alkali and pure water, and finally dehydrating to obtain a wet material with the moisture content of about 10%.
(6) And drying the nickel cobalt hydroxide wet material at the temperature of 120 ℃ by using an oven to finally obtain a nickel cobalt hydroxide product.
(7) The nickel cobalt hydroxide is put into a kiln, the feeding quantity of the kiln is controlled to be 300kg/h and the air inlet quantity and the air outlet quantity of the kiln are controlled to be 600m at 600 DEG C3And h, preparing the nickel-cobalt oxide with special pores under the condition that the rotation speed of the kiln is 2 r/min.
FIG. 2 is a plot of the multiple narrow peak analytical particle size distribution of the nickel cobalt hydroxide obtained in example 1; FIG. 3 is a multi-narrow-peak analytical particle size distribution diagram of the nickel cobalt oxide obtained in example 1; FIG. 4 is an XRD pattern of nickel cobalt hydroxide obtained in example 1; fig. 5 is an XRD pattern of the nickel cobalt oxide obtained in example 1.
Fig. 6 is a surface electron micrograph of the nickel cobalt hydroxide obtained in example 1, and fig. 7 is a sectional electron micrograph of the nickel cobalt hydroxide obtained in example 1. As can be seen from fig. 6 and 7, the nickel-cobalt hydroxide product obtained in example 1 has a smooth and dense surface appearance, and the primary particles grow from inside to outside; the interior of the product is of a three-layer structure, and the product sequentially comprises an inner core area, a middle area and an outer shell area from inside to outside.
Fig. 8 is a surface electron micrograph of the nickel cobalt oxide obtained in example 1, fig. 9 is a sectional electron micrograph of the nickel cobalt oxide obtained in example 1, and fig. 10 is a high-power sectional electron micrograph of the nickel cobalt oxide obtained in example 1. As can be seen from fig. 8 to 10, the nickel-cobalt oxide obtained in example 1 has a smooth and dense surface morphology, and primary particles are criss-cross and have microcracks; the first area, the second area and the third area are arranged from inside to outside in sequence.
Example 2
(1) Dissolving a certain amount of nickel sulfate crystals and cobalt sulfate crystals in water, and mixing to prepare a mixed metal salt solution with a nickel-cobalt ratio of 93:7 and a metal concentration of 110 g/L.
(2) Adding 8m into a reaction kettle3Water andadjusting the pH value to 12.0 by using a proper amount of liquid alkali and ammonia water, starting the reaction at a rotating speed of 200r/min, wherein the flow rate of the binary solution is 400L/h, the flow rate of the liquid alkali is 200L/h, the flow rate of the ammonia water is 30L/h, and carrying out coprecipitation reaction under the condition of keeping the reaction temperature at 60 ℃ to obtain the crystal seeds with the particle size of 5.0 microns.
(3) And (4) dehydrating and spin-drying the seed crystal by using a centrifugal machine to obtain the seed crystal wet material with the water content of about 20%.
(4) Adopting a batch method for reaction, putting 150kg of seed crystal into a reaction kettle added with liquid alkali and ammonia water, starting the reaction at the rotating speed of 200r/min, wherein the flow rate of the binary solution is 500L/h, the flow rate of the liquid alkali is 200L/h, the flow rate of the ammonia water is 30L/h, keeping the conditions of the reaction temperature of 50 ℃ and the pH value of 10.5, carrying out coprecipitation reaction, enabling the seed crystal to slowly grow, and adjusting the pH value to 11.4 at the later stage (3d-5d) to prepare the nickel-cobalt hydroxide with the particle size of 16 mu m.
(5) And respectively carrying out alkaline washing and water washing on the nickel-cobalt hydroxide slurry by using 10% diluted alkali and pure water, and finally dehydrating to obtain a wet material with the moisture content of about 10%.
(6) And drying the nickel cobalt hydroxide wet material at the temperature of 120 ℃ by using an oven to finally obtain a nickel cobalt hydroxide product.
(7) The nickel cobalt hydroxide is put into a kiln, the feeding quantity of the kiln is controlled to be 300kg/h and the air inlet quantity and the air outlet quantity of the kiln are controlled to be 600m at 600 DEG C3And h, preparing the nickel-cobalt oxide with special pores under the condition that the rotation speed of the kiln is 2 r/min.
Example 3
(1) Dissolving a certain amount of nickel sulfate crystals and cobalt sulfate crystals in water, and mixing to prepare a mixed metal salt solution with the nickel-cobalt ratio of 92:8 and the metal concentration of 110 g/L.
(2) Adding 8m into a reaction kettle3Adjusting the pH value of water and a proper amount of liquid caustic soda and ammonia water to 12.0, starting reaction at a rotating speed of 200r/min, wherein the flow rate of the binary solution is 400L/h, the flow rate of the liquid caustic soda is 200L/h, the flow rate of the ammonia water is 30L/h, and carrying out coprecipitation reaction under the condition of keeping the reaction temperature at 60 ℃ to obtain the crystal seeds with the particle size of 5.0 microns.
(3) And (4) dehydrating and spin-drying the seed crystal by using a centrifugal machine to obtain the seed crystal wet material with the water content of about 20%.
(4) Adopting a batch method for reaction, putting 150kg of seed crystal into a reaction kettle added with liquid alkali and ammonia water, starting the reaction at the rotating speed of 200r/min, wherein the flow rate of the binary solution is 300L/h, the flow rate of the liquid alkali is 150L/h, the flow rate of the ammonia water is 25L/h, keeping the conditions of the reaction temperature of 50 ℃ and the pH value of 10.5, carrying out coprecipitation reaction, enabling the seed crystal to slowly grow, and adjusting the pH value to 11.4 at the later stage (3d-5d) to prepare the nickel-cobalt hydroxide with the particle size of 16 mu m.
(5) And respectively carrying out alkaline washing and water washing on the nickel-cobalt hydroxide slurry by using 10% diluted alkali and pure water, and finally dehydrating to obtain a wet material with the moisture content of about 10%.
(6) And drying the nickel cobalt hydroxide wet material at the temperature of 120 ℃ by using an oven to finally obtain a nickel cobalt hydroxide product.
(7) The nickel cobalt hydroxide is put into a kiln, the feeding quantity of the kiln is controlled to be 300kg/h and the air inlet quantity and the air outlet quantity of the kiln are controlled to be 600m at 600 DEG C3And h, preparing the nickel-cobalt oxide with special pores under the condition that the rotation speed of the kiln is 2 r/min.
Example 4
(1) Dissolving a certain amount of nickel sulfate crystals and cobalt sulfate crystals in water, and mixing to prepare a mixed metal salt solution with the nickel-cobalt ratio of 92:8 and the metal concentration of 110 g/L.
(2) Adding 8m into a reaction kettle3Adjusting the pH value of water and a proper amount of liquid caustic soda and ammonia water to 12.0, starting reaction at a rotating speed of 200r/min, wherein the flow rate of the binary solution is 400L/h, the flow rate of the liquid caustic soda is 200L/h, the flow rate of the ammonia water is 30L/h, and carrying out coprecipitation reaction under the condition of keeping the reaction temperature at 60 ℃ to obtain the crystal seeds with the particle size of 5.0 microns.
(3) And (4) dehydrating and spin-drying the seed crystal by using a centrifugal machine to obtain the seed crystal wet material with the water content of about 20%.
(4) Adopting a batch method for reaction, putting 150kg of seed crystal into a reaction kettle added with liquid alkali and ammonia water, starting the reaction at the rotating speed of 200r/min, wherein the flow rate of the binary solution is 500L/h, the flow rate of the liquid alkali is 200L/h, the flow rate of the ammonia water is 30L/h, keeping the conditions of the reaction temperature of 50 ℃ and the pH value of 10.7, carrying out coprecipitation reaction, enabling the seed crystal to slowly grow, and adjusting the pH value to 11.8 at the later stage (3d-5d) to prepare the nickel-cobalt hydroxide with the particle size of 16 mu m.
(5) And respectively carrying out alkaline washing and water washing on the nickel-cobalt hydroxide slurry by using 10% diluted alkali and pure water, and finally dehydrating to obtain a wet material with the moisture content of about 10%.
(6) And drying the nickel cobalt hydroxide wet material at the temperature of 120 ℃ by using an oven to finally obtain a nickel cobalt hydroxide product.
(7) The nickel cobalt hydroxide is put into a kiln, the feeding quantity of the kiln is controlled to be 300kg/h and the air inlet quantity and the air outlet quantity of the kiln are controlled to be 600m at 600 DEG C3And h, preparing the nickel-cobalt oxide with special pores under the condition that the rotation speed of the kiln is 2 r/min.
Example 5
(1) Dissolving a certain amount of nickel sulfate crystals and cobalt sulfate crystals in water, and mixing to prepare a mixed metal salt solution with the nickel-cobalt ratio of 92:8 and the metal concentration of 110 g/L.
(2) Adding 8m into a reaction kettle3Adjusting the pH value of water and a proper amount of liquid caustic soda and ammonia water to 12.0, starting reaction at a rotating speed of 200r/min, wherein the flow rate of the binary solution is 400L/h, the flow rate of the liquid caustic soda is 200L/h, the flow rate of the ammonia water is 30L/h, and carrying out coprecipitation reaction under the condition of keeping the reaction temperature at 60 ℃ to obtain the crystal seeds with the particle size of 5.0 microns.
(3) And (4) dehydrating and spin-drying the seed crystal by using a centrifugal machine to obtain the seed crystal wet material with the water content of about 20%.
(4) Adopting a batch method for reaction, putting 150kg of seed crystal into a reaction kettle added with liquid alkali and ammonia water, starting the reaction at the rotating speed of 180r/min, wherein the flow rate of the binary solution is 500L/h, the flow rate of the liquid alkali is 200L/h, the flow rate of the ammonia water is 30L/h in the reaction process, keeping the conditions of the reaction temperature of 50 ℃ and the pH value of 10.5, carrying out coprecipitation reaction, enabling the seed crystal to slowly grow, and adjusting the pH value to 11.4 in the later period (3d-5d) to prepare the nickel-cobalt hydroxide with the particle size of 16 mu m.
(5) And respectively carrying out alkaline washing and water washing on the nickel-cobalt hydroxide slurry by using 10% diluted alkali and pure water, and finally dehydrating to obtain a wet material with the moisture content of about 10%.
(6) And drying the nickel cobalt hydroxide wet material at the temperature of 120 ℃ by using an oven to finally obtain a nickel cobalt hydroxide product.
(7) The nickel cobalt hydroxide is put into a kiln, the feeding quantity of the kiln is controlled to be 300kg/h and the air inlet quantity and the air outlet quantity of the kiln are controlled to be 600m at 600 DEG C3And h, preparing the nickel-cobalt oxide with special pores under the condition that the rotation speed of the kiln is 2 r/min.
Comparative example 1
(1) Dissolving a certain amount of nickel sulfate crystals and cobalt sulfate crystals in water, and mixing to prepare a mixed metal salt solution with the nickel-cobalt ratio of 92:8 and the metal concentration of 110 g/L.
(2) Adding 8m into a reaction kettle3Adjusting the pH value of water and a proper amount of liquid caustic soda and ammonia water to 12.0, starting reaction at a rotating speed of 200r/min, wherein the flow rate of the binary solution is 400L/h, the flow rate of the liquid caustic soda is 200L/h, the flow rate of the ammonia water is 30L/h, and carrying out coprecipitation reaction under the condition of keeping the reaction temperature at 60 ℃ to obtain the crystal seeds with the particle size of 5.0 microns.
(3) And (4) dehydrating and spin-drying the seed crystal by using a centrifugal machine to obtain the seed crystal wet material with the water content of about 20%.
(4) And (2) adopting a batch method for reaction, putting 150kg of seed crystals into a reaction kettle added with liquid alkali and ammonia water, starting the reaction at the rotating speed of 200r/min, wherein the flow rate of the binary solution is 500L/h, the flow rate of the liquid alkali is 200L/h, the flow rate of the ammonia water is 30L/h, keeping the conditions (whole process) of the reaction temperature of 50 ℃ and the pH value of 10.5, carrying out coprecipitation reaction, and slowly growing the seed crystals to prepare the nickel-cobalt hydroxide with the particle size of 16 mu m.
(5) And respectively carrying out alkaline washing and water washing on the nickel-cobalt hydroxide slurry by using 10% diluted alkali and pure water, and finally dehydrating to obtain a wet material with the moisture content of about 10%.
(6) And drying the nickel cobalt hydroxide wet material at the temperature of 120 ℃ by using an oven to finally obtain a nickel cobalt hydroxide product.
(7) The nickel cobalt hydroxide is put into a kiln, the feeding quantity of the kiln is controlled to be 300kg/h and the air inlet quantity and the air outlet quantity of the kiln are controlled to be 600m at 600 DEG C3And h, preparing the nickel-cobalt oxide with special pores under the condition that the rotation speed of the kiln is 2 r/min.
Comparative example 2
(1) Dissolving a certain amount of nickel sulfate crystals and cobalt sulfate crystals in water, and mixing to prepare a mixed metal salt solution with the nickel-cobalt ratio of 92:8 and the metal concentration of 110 g/L.
(2) Adding 8m into a reaction kettle3Adjusting the pH value of water and a proper amount of liquid caustic soda and ammonia water to 12.0, starting reaction at a rotating speed of 200r/min, wherein the flow rate of the binary solution is 400L/h, the flow rate of the liquid caustic soda is 200L/h, the flow rate of the ammonia water is 30L/h, and carrying out coprecipitation reaction under the condition of keeping the reaction temperature at 60 ℃ to obtain the crystal seeds with the particle size of 5.0 microns.
(3) And (4) dehydrating and spin-drying the seed crystal by using a centrifugal machine to obtain the seed crystal wet material with the water content of about 20%.
(4) And (2) adopting a batch method for reaction, putting 150kg of seed crystals into a reaction kettle added with liquid alkali and ammonia water, starting the reaction at the rotating speed of 200r/min, wherein the flow rate of the binary solution is 500L/h, the flow rate of the liquid alkali is 200L/h, the flow rate of the ammonia water is 30L/h, keeping the conditions (whole process) of the reaction temperature of 50 ℃ and the pH value of 11.4, carrying out coprecipitation reaction, and slowly growing the seed crystals to prepare the nickel-cobalt hydroxide with the particle size of 16 mu m.
(5) And respectively carrying out alkaline washing and water washing on the nickel-cobalt hydroxide slurry by using 10% diluted alkali and pure water, and finally dehydrating to obtain a wet material with the moisture content of about 10%.
(6) And drying the nickel cobalt hydroxide wet material at the temperature of 120 ℃ by using an oven to finally obtain a nickel cobalt hydroxide product.
(7) The nickel cobalt hydroxide is put into a kiln, the feeding quantity of the kiln is controlled to be 300kg/h and the air inlet quantity and the air outlet quantity of the kiln are controlled to be 600m at 600 DEG C3And h, preparing the nickel-cobalt oxide with special pores under the condition that the rotation speed of the kiln is 2 r/min.
Comparative example 3
(1) Dissolving a certain amount of nickel sulfate crystals and cobalt sulfate crystals in water, and mixing to prepare a mixed metal salt solution with the nickel-cobalt ratio of 92:8 and the metal concentration of 110 g/L.
(2) Adding 8m into a reaction kettle3Water, a proper amount of liquid caustic soda and ammonia water are added, the pH value is adjusted to 12.0, and then the reaction is started at the rotating speed of 200r/minIn the reaction process, the flow rate of the binary solution is 400L/h, the flow rate of the liquid caustic soda is 200L/h, the flow rate of the ammonia water is 30L/h, and the coprecipitation reaction is carried out under the condition that the reaction temperature is kept at 60 ℃ to obtain the crystal seeds with the particle size of 5.0 mu m.
(3) And (4) dehydrating and spin-drying the seed crystal by using a centrifugal machine to obtain the seed crystal wet material with the water content of about 20%.
(4) Adopting a batch method for reaction, putting 150kg of seed crystal into a reaction kettle added with liquid alkali and ammonia water, starting the reaction at the rotating speed of 200r/min, wherein the flow rate of the binary solution is 500L/h, the flow rate of the liquid alkali is 200L/h, the flow rate of the ammonia water is 30L/h, keeping the conditions of the reaction temperature of 50 ℃ and the pH value of 11.4, carrying out coprecipitation reaction, enabling the seed crystal to slowly grow, and adjusting the pH value to 10.5 at the later stage (3d-5d) to prepare the nickel-cobalt hydroxide with the particle size of 16 mu m.
(5) And respectively carrying out alkaline washing and water washing on the nickel-cobalt hydroxide slurry by using 10% diluted alkali and pure water, and finally dehydrating to obtain a wet material with the moisture content of about 10%.
(6) And drying the nickel cobalt hydroxide wet material at the temperature of 120 ℃ by using an oven to finally obtain a nickel cobalt hydroxide product.
(7) The nickel cobalt hydroxide is put into a kiln, the feeding quantity of the kiln is controlled to be 300kg/h and the air inlet quantity and the air outlet quantity of the kiln are controlled to be 600m at 600 DEG C3And h, preparing the nickel-cobalt oxide with special pores under the condition that the rotation speed of the kiln is 2 r/min.
Comparative example 4
(1) Dissolving a certain amount of nickel sulfate crystals and cobalt sulfate crystals in water, and mixing to prepare a mixed metal salt solution with the nickel-cobalt ratio of 92:8 and the metal concentration of 110 g/L.
(2) Adding 8m into a reaction kettle3Adjusting the pH value of water and a proper amount of liquid caustic soda and ammonia water to 12.0, starting reaction at a rotating speed of 200r/min, wherein the flow rate of the binary solution is 400L/h, the flow rate of the liquid caustic soda is 200L/h, the flow rate of the ammonia water is 30L/h, and carrying out coprecipitation reaction under the condition of keeping the reaction temperature at 60 ℃ to obtain the crystal seeds with the particle size of 5.0 microns.
(3) And (4) dehydrating and spin-drying the seed crystal by using a centrifugal machine to obtain the seed crystal wet material with the water content of about 20%.
(4) Adopting a batch method for reaction, putting 150kg of seed crystal into a reaction kettle added with liquid alkali and ammonia water, starting the reaction at the rotating speed of 200r/min, wherein the flow rate of the binary solution is 500L/h, the flow rate of the liquid alkali is 200L/h, the flow rate of the ammonia water is 30L/h, keeping the conditions of the reaction temperature of 50 ℃ and the pH value of 10.5, carrying out coprecipitation reaction, enabling the seed crystal to slowly grow, and adjusting the pH value to 11.4 at the later stage (4d-5d) to prepare the nickel-cobalt hydroxide with the particle size of 16 mu m.
(5) And respectively carrying out alkaline washing and water washing on the nickel-cobalt hydroxide slurry by using 10% diluted alkali and pure water, and finally dehydrating to obtain a wet material with the moisture content of about 10%.
(6) And drying the nickel cobalt hydroxide wet material at the temperature of 120 ℃ by using an oven to finally obtain a nickel cobalt hydroxide product.
(7) The nickel cobalt hydroxide is put into a kiln, the feeding quantity of the kiln is controlled to be 300kg/h and the air inlet quantity and the air outlet quantity of the kiln are controlled to be 600m at 600 DEG C3And h, preparing the nickel-cobalt oxide with special pores under the condition that the rotation speed of the kiln is 2 r/min.
FIG. 11 is a sectional electron micrograph of a nickel cobalt hydroxide obtained in comparative examples 1 to 4. Wherein, the upper left corresponds to comparative example 1, the upper right corresponds to comparative example 2, the lower left corresponds to comparative example 3, and the lower right corresponds to comparative example 4.
The hydroxide materials obtained in examples 1 to 5 and comparative examples 1 to 4 were prepared into half cells and tested, and the results are shown in the following tables 1, 2 and 3:
table 1 results of material testing
Table 2 results of material testing
After a plurality of tests, the (D95-D5)/D50 of the nickel cobalt hydroxide obtained by the preparation method provided by the application is 0.35-0.5, and the (D95-D5)/D50 of the nickel cobalt oxide is 0.18-0.32; the peak intensity ratio (I101: I001) of the nickel cobalt hydroxide is 1.1 or more, preferably 1.2 to 1.5, the half width at 001 of 0.5 to 0.9, and the half width at 101 of 0.45 to 0.85; the nickel-cobalt oxide has a peak intensity ratio (I012: I101) of not less than 1.4, a half-width at 101 of 0.50-0.85, and a half-width at 012 of 0.60-0.95.
The average data is obtained by measuring the nickel-cobalt hydroxide for many times, the diameter of an inner core area is 3-6 mu m, the inner core area is of a porous structure, no stripe crack exists, and the porosity is 1% -5%; the diameter of the middle area is 5-14 μm, the middle area is of a porous structure and is provided with radial stripes, and the porosity is 5% -10%; the diameter of the shell area is 10-16 mu m, the shell area is of a porous structure, no stripe crack exists, and the porosity is 1% -5%.
The nickel-cobalt oxide obtained by the method is measured for many times to obtain average data, the diameter of the first region is 3-6 mu m, the first region is of a porous structure, a small amount of stripe cracks exist, and the porosity is 3% -10%; the width of the stripe is 0-0.05 μm; the diameter of the second area is 5-14 μm, the second area is a porous structure and has special radial stripes, the porosity is 15% -25%, and the width of the stripes is 0-0.25 μm; the diameter of the third area is 10-16 μm, the third area is a porous structure, a small amount of stripe cracks exist, the porosity is 5% -15%, and the stripe width is 0-0.05 μm.
In order to evaluate the characteristics of the porosity, the porosity of each region is calculated by directly determining the pore area and the cross-sectional area of each region by using image analysis software (ImageJ), and the porosity of each region is calculated by multiplying the porosity by the pore area of each region/the cross-sectional area of each region by 100%.
TABLE 3 Battery Performance test results
As can be seen from tables 1, 2 and 3 above, the half cells prepared from the materials obtained in the examples have an average 0.1C first charge capacity of about 245mAh/g, which is about 20mAh/g higher than the comparative example. The average value of the first discharge capacity of 0.1C is about 214mAh/g, which is about 15mAh/g higher than that of the comparative example. The average value of the capacity retention rate after 50 weeks of 1C circulation is about 97 percent, which is about 8 percent higher than that of the comparative example. The mean value of the rate performance (1C/0.1C) is about 93 percent, and the ratio is about 6 percent higher.
Meanwhile, as can be shown by comparing example 1 with comparative examples 1, 2, 3 and 4, the pH control in the former stage (0 to 2d) and the latter stage (3d to 5d) has a large influence on the structure of the product in the process of preparing the nickel cobalt hydroxide by the batch method in step 4.
Therefore, the hydroxide material with the special pore structure provided by the application can obviously improve the battery capacity, the cycle performance and the rate performance compared with the hydroxide material with the general structure.
Finally, it should be noted that: the above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (12)
1. A nickel cobalt hydroxide comprising an inner core region, an intermediate region, and an outer shell region, wherein the intermediate region encapsulates the inner core region and the outer shell region encapsulates the intermediate region;
the porosity of the intermediate region is greater than the porosity of the inner core region and the porosity of the shell region.
2. The nickel cobalt hydroxide of claim 1 wherein the nickel cobalt hydroxide satisfies at least one of the following conditions:
a. the porosity of the intermediate zone is 5% -10%, and the porosity of the inner core zone and the porosity of the outer shell zone are respectively and independently 1% -5%;
b. the pores of the inner core area are distributed in a network shape, the pores of the middle area are radially dispersed to the shell area, and the pores of the shell area are distributed in a scattered point shape;
c. the diameter of the inner core area is 3-6 μm;
d. the diameter of the middle area is 5-14 μm;
e. the diameter of the shell area is 10-16 μm;
f. the peak intensity ratio (I101: I001) of the nickel cobalt hydroxide is not less than 1.1;
g. the nickel cobalt hydroxide has a peak intensity ratio (I101: I001) of 1.2 to 1.5;
h. the 001 half-peak width of the nickel-cobalt hydroxide is 0.5-0.9, and the 101 half-peak width is 0.45-0.85;
i. the nickel cobalt hydroxide has (D95-D5)/D50 of 0.35-0.5.
3. The nickel-cobalt hydroxide according to claim 1 or 2, characterized in that it has the formula NixCo(1-x)(OH)2Wherein x is more than or equal to 0.8<1.0。
4. A method of preparing the nickel cobalt hydroxide according to any one of claims 1 to 3, comprising:
mixing raw materials including a nickel-cobalt binary aqueous solution, a sodium hydroxide aqueous solution and ammonia water, and obtaining seed crystals through a first coprecipitation reaction;
and mixing the raw materials including the seed crystal, the nickel-cobalt binary aqueous solution, the sodium hydroxide aqueous solution and ammonia water, and carrying out a second coprecipitation reaction to obtain the nickel-cobalt hydroxide.
5. The production method according to claim 4, wherein the production method satisfies at least one of the following conditions:
j. the concentration of the nickel-cobalt binary aqueous solution is 80g/L-120 g/L;
k. in the processes of the first coprecipitation reaction and the second coprecipitation reaction, the flow rates of the nickel-cobalt binary aqueous solution and the aqueous solution of the sodium hydroxide are respectively 300L/h-600L/h independently, the flow rates of the aqueous solution of the sodium hydroxide are respectively 60L/h-250L/h independently, and the flow rates of the aqueous solution of the ammonia are respectively 10L/h-50L/h independently;
in the processes of the first coprecipitation reaction and the second coprecipitation reaction, the temperature is 40-60 ℃ respectively and the stirring speed is 180-220 r/min respectively;
m. during the first coprecipitation reaction, the pH is between 10 and 13; in the process of the second coprecipitation reaction, the pH control range of the system is as follows: the pH value is 10.3-10.8 within 2 days after the reaction, and the pH value is 11.4-12 after the reaction is carried out for 3 days until the reaction is finished;
n, the grain size of the seed crystal is 3-7 μm;
o. after the first coprecipitation reaction is finished, obtaining the seed crystal with the moisture content of less than or equal to 25% through solid-liquid separation;
p. the particle size of the nickel cobalt hydroxide is not less than 12 μm;
q. after the second co-precipitation reaction further comprising: sequentially carrying out alkali washing, water washing, solid-liquid separation and drying on a reaction product;
the concentration of the sodium hydroxide aqueous solution used for alkaline washing is 3-10 wt%; the drying temperature is 90-150 ℃.
6. A nickel cobalt oxide comprising a first region, a second region, and a third region, the second region encapsulating the first region, the third region encapsulating the second region;
the porosity of the second region is greater than the porosity of the first region, and the porosity of the second region is greater than or equal to the porosity of the third region.
7. The nickel cobalt oxide of claim 6, wherein the nickel cobalt oxide satisfies at least one of the following conditions:
r. the porosity of the first region is 3% to 10%, the porosity of the second region is 15% to 25%, and the porosity of the third region is 5% to 15%;
s. the diameter of the first region is from 3 μm to 6 μm, the diameter of the second region is from 5 μm to 14 μm, and the diameter of the third region is from 10 μm to 16 μm;
t. the nickel cobalt oxide has (D95-D5)/D50 of 0.18-0.32;
u. the nickel cobalt oxide has a peak intensity ratio (I012: I101) of not less than 1.4, a 101 half-peak width of 0.50-0.85, and a 012 half-peak width of 0.60-0.95;
v. the molecular formula of the nickel cobalt oxide is NiyCo(1-y)O, wherein y is more than or equal to 0.8<1.0。
8. The nickel cobalt oxide of claim 6 or 7, wherein the nickel cobalt oxide is fired using a nickel cobalt hydroxide comprising an inner core region, an intermediate region, and an outer shell region, the intermediate region encasing the inner core region and the outer shell region encasing the intermediate region; the porosity of the intermediate region is greater than the porosity of the inner core region and the porosity of the shell region;
preferably, the firing satisfies at least one of the following conditions:
the firing temperature is 400-600 ℃;
x, in the firing process, the feeding amount of the kiln is 200kg/h-500kg/h, and the air inlet and outlet amount of the kiln is 400m3/h-600m3The rotation speed of the kiln is 1r/min-6 r/min.
9. A positive electrode material for a lithium ion battery, characterized in that a raw material thereof comprises the nickel cobalt hydroxide according to any one of claims 1 to 3 or the nickel cobalt oxide according to any one of claims 6 to 8.
10. A positive electrode for a lithium ion battery, characterized in that the raw material thereof comprises the positive electrode material for a lithium ion battery according to claim 9.
11. A lithium ion battery comprising the positive electrode for a lithium ion battery according to claim 10.
12. An electric device comprising or powered by the lithium ion battery of claim 11.
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