CN115676909B - Cobalt carbonate precursor and preparation method and application thereof - Google Patents
Cobalt carbonate precursor and preparation method and application thereof Download PDFInfo
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- 229910021446 cobalt carbonate Inorganic materials 0.000 title claims abstract description 189
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 title claims abstract description 189
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002243 precursor Substances 0.000 title abstract description 23
- 239000011247 coating layer Substances 0.000 claims abstract description 74
- 239000002245 particle Substances 0.000 claims abstract description 67
- 239000011159 matrix material Substances 0.000 claims abstract description 42
- 238000001354 calcination Methods 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims description 104
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 238000000576 coating method Methods 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 42
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 39
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 25
- 239000012670 alkaline solution Substances 0.000 claims description 23
- 238000000975 co-precipitation Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims 6
- 239000010410 layer Substances 0.000 claims 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims 1
- 238000005204 segregation Methods 0.000 abstract description 18
- 238000005336 cracking Methods 0.000 abstract description 11
- 239000007774 positive electrode material Substances 0.000 abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002345 surface coating layer Substances 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000000051 modifying effect Effects 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000003405 preventing effect Effects 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000003887 surface segregation Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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 invention provides a cobalt carbonate precursor, a preparation method and application thereof, wherein cobalt carbonate comprises an Al-doped cobalt carbonate matrix and a cobalt carbonate coating layer coated on the surface of the Al-doped cobalt carbonate matrix, and the cobalt carbonate coating layer contains Al and other doping elements. According to the invention, the surface of the Al-doped cobalt carbonate matrix is coated with the cobalt carbonate coating layer containing Al and other doped elements, and after calcination, the elements of the surface coating layer and the matrix elements are mutually diffused to form the multifunctional surface gradient coating layer, so that not only can the aluminum segregation on the surfaces of particles be effectively inhibited, the cracking of the particles during calcination be prevented, the surface morphology is improved, but also the corrosion of the positive electrode material by electrolyte can be effectively avoided, and the cycle and the multiplying power performance of the battery are improved.
Description
Technical Field
The invention belongs to the technical field of positive electrode materials, and particularly relates to a cobalt carbonate precursor, a preparation method and application thereof.
Background
Lithium cobaltate is widely applied to 3C digital electronic products, and along with the diversification of functions of portable equipment and diversification of use scenes, the energy density requirement of the market on a lithium cobaltate battery is higher and higher, and the common process in industry at present is to increase the energy density of the battery by doping element Al to improve the charging voltage of the anode material.
The method for doping Al is various, al salt can be added in the preparation Li calcination stage for mixed calcination, or Al salt can be added in the cobalt carbonate synthesis stage for element doping through coprecipitation, so that the method is simple, the content is controllable, and the method is widely applied. However, with higher and higher amounts of Al, problems of flaky segregation and calcination cracking of the particle surface during the reaction, washing and calcination are mostly solved by improving the surface morphology or increasing the reaction temperature.
CN113307308a discloses a doped large-particle cobalt carbonate and a preparation method thereof, wherein the large-particle cobalt carbonate is doped with metal elements, the shape of primary particles is conical, the primary particles form spherical secondary particles, and the preparation method comprises the steps of nucleation, concentration, seed crystal kettle in-growth and seed crystal kettle-division growth. The doped large-particle cobalt carbonate has higher crystallinity, is favorable for the uniform distribution of doped element aluminum, has higher tap density and narrower particle size distribution, and is favorable for reducing the aluminum segregation phenomenon. However, this applies only to the low concentration Al doping method.
CN114014374a discloses a preparation method and application of a cobalt carbonate composite precursor with a core-shell structure and a sintered lithium cobalt oxide coating, and the method is realized through the following steps: 1) Solution preparation and synthesis; 2) Primary sintering; 3) Secondary sintering; 4) Ball milling; 5) And sintering for three times to obtain the lithium cobalt oxide coating the CNTs and the core-shell structure. However, the coating obtained by the method is uneven and inconsistent with the lattice structure of the matrix, so that the coating is easy to fall off, and the body performance is affected by three times of sintering.
Therefore, how to inhibit aluminum segregation, avoid poor morphology and calcination cracking caused by high aluminum doping is a technical problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a cobalt carbonate precursor, and a preparation method and application thereof. The invention provides a cobalt carbonate precursor with a cobalt carbonate coating layer, which takes cobalt carbonate as a matrix, and the surface of the cobalt carbonate precursor comprises the cobalt carbonate coating layer containing a first doping element. After calcination, the elements of the cobalt oxide surface coating layer and the matrix elements are mutually diffused to form a multifunctional surface gradient coating, so that not only can the aluminum segregation on the particle surface be effectively inhibited, the cracking of the particles during calcination is prevented, the surface morphology is improved, but also the corrosion of the positive electrode material by electrolyte can be effectively avoided, and the cycle and the multiplying power performance of the battery are improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
In a first aspect, the invention provides a cobalt carbonate, which comprises an Al-doped cobalt carbonate matrix and a cobalt carbonate coating layer coated on the surface of the Al-doped cobalt carbonate matrix, wherein the cobalt carbonate coating layer contains Al and other doping elements.
The invention provides a cobalt carbonate precursor which takes aluminum doped cobalt carbonate as a matrix and has the surface of a cobalt carbonate coating layer containing Al element and other doping elements. The coating layer containing the Al element can effectively prevent segregation of Al in the matrix, and the particle structure is protected and corresponding functions are provided by supplementing other elements instead of Al, so that the multifunctional surface coating layer is obtained, the Li transmission speed of the anode material can be accelerated, the capacity can be improved, the electrolyte corrosion can be relieved, and the circulation and rate performance can be improved.
In the invention, if the surface of the cobalt carbonate matrix is not coated with the cobalt carbonate coating layer, the surface of the particles can have the problems of local flaky Al segregation, particle cracking and the like in the subsequent calcination stage.
It should be noted that the main composition of the surface coating layer contains cobalt carbonate, and if a pure doping element compound is substituted as the coating layer, the lattice difference becomes too large, the coating layer is liable to fall off, and the capacity of the positive electrode material is reduced.
Preferably, the other doping elements in the cobalt carbonate coating layer comprise any one or a combination of at least two of Mn, ni, mg, zr or La.
Preferably, the Al doping amount in the Al doped cobalt carbonate matrix is 8000ppm to 20000ppm, for example 8000ppm、9000ppm、10000ppm、11000ppm、12000ppm、13000ppm、14000ppm、15000ppm、16000ppm、17000ppm、18000ppm、19000ppm or 20000ppm, etc.
Preferably, the content of Al in the cobalt carbonate coating layer is 10-50%, for example 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50% of the Al doping amount in the Al-doped cobalt carbonate matrix, based on 100% by mass of the cobalt carbonate coating layer.
In the present invention, if the content of Al element in the cobalt carbonate coating layer is too small, the modifying effect on the material is weakened, and if the content is too large, the segregation preventing effect is not exerted.
Preferably, the content of the other doping elements in the cobalt carbonate coating layer is the difference between the Al doping amount in the cobalt carbonate substrate and the Al content in the cobalt carbonate coating layer, based on 100% of the mass of the cobalt carbonate substrate. If the content of other doping elements in the cobalt carbonate coating layer is larger than the difference value, the specific capacity of the material is reduced; the content of other doping elements in the cobalt carbonate coating layer is smaller than the above difference, which results in reduced supporting effect and reduced capacity, initial efficiency and cycle performance of the battery prepared by using the cobalt carbonate coating layer.
Preferably, the content of other doping elements in the cobalt carbonate coating layer is 50% -90%, such as 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% of the Al doping amount in the Al-doped cobalt carbonate matrix.
Preferably, the content of other doping elements in the cobalt carbonate matrix is less than 0.05%, for example 0.01%, 0.02%, 0.03%, or 0.04%, etc., based on 100% by mass of the Al-doped cobalt carbonate matrix.
Preferably, the thickness of the cobalt carbonate coating layer is 1-2 μm, for example 1 μm, 1.5 μm or 2 μm, etc.
In the invention, if the thickness of the cobalt carbonate coating layer is too thin, the cobalt carbonate coating layer is easy to fall off in the calcining process, the segregation and cracking problems cannot be effectively inhibited, and if the thickness is too thick, the electrochemical performance of the machine body is affected.
In a second aspect, the present invention provides a process for the preparation of cobalt carbonate as described in the first aspect, the process comprising:
Co-precipitation reaction is carried out on metal solution containing Co and Al and alkaline solution to prepare cobalt carbonate, when cobalt carbonate particles grow to be close to a preset particle size, any operation of (a) or (b) is carried out, and then the reaction is continued to obtain cobalt carbonate,
(A) Changing the metal solution into a first coating liquid, wherein the components of the first coating liquid comprise: cobalt salt solution, al and other doping elements;
(b) And replacing part of the metal solution to obtain a mixed coating solution, wherein the components of the second coating solution comprise Al and other doping elements.
In the invention, a metal solution containing Co and Al and an alkaline solution are used as raw materials of a cobalt carbonate precursor, the raw materials are added into a reaction container for coprecipitation reaction, when the particle size of cobalt carbonate particles grows to be close to a preset particle size, the metal solution containing Co and Al is completely replaced by a first coating solution containing cobalt salt solution, al and other doping elements, or part of the metal solution containing Co and Al is replaced by a second coating solution containing Al and other doping elements, and the coprecipitation reaction is continued, so that the cobalt carbonate precursor with the preset particle size is finally obtained. The coating process is realized by replacing raw materials in the coprecipitation reaction process, so that not only can the segregation of Al be prevented, but also the complete coating can be realized on the surface of the cobalt carbonate matrix, the complete coverage is realized, and the better protection effect is realized.
Preferably, the near-preset particle size is: the difference between the preset particle diameter and the actual particle diameter is 1 to 2 μm, for example, 1 μm, 1.5 μm, 2 μm, or the like.
In the present invention, if the difference between the preset particle size and the actual particle size is too large, the thickness of the coating layer is affected.
Preferably, the method for preparing cobalt carbonate by coprecipitation reaction of a metal solution containing Co and Al and an alkaline solution comprises the following steps:
(1) Preparing a metal solution, an alkaline solution and a base solution containing Co and Al respectively;
(2) Adding a base solution into a reaction vessel, adding a metal solution containing Co and Al and an alkaline solution in a parallel flow mode, and performing coprecipitation reaction.
The preparation sequence of the cobalt-containing solution, the alkaline solution and the base solution is not limited, and the solution can be prepared sequentially or synchronously.
In one embodiment, the base solution is first placed inside a vessel, and the Co-and Al-containing metal solution and the alkaline solution are added to the vessel in a Co-current manner to effect the Co-precipitation reaction. Along with the continuous progress of the reaction, the particles grow up, the particle size gradually approaches to the preset particle size, when the particle size approaches to the preset particle size, part of the metal solution containing Co and Al is replaced to be the second coating solution, at the moment, the mixed solution of the second coating solution and the cobalt-containing solution and the alkaline solution are continuously added into a container for reaction, and finally the cobalt carbonate precursor with the preset particle size is obtained, and the cobalt carbonate coating layer containing Al and other doping elements is formed on the surface of the cobalt carbonate substrate.
Preferably, the Co-containing solution comprises any one or a combination of at least two of CoCl 2、CoSO4 or CoNO 3.
Preferably, the Al-containing compound comprises any one or a combination of at least two of AlCl, alSO 4 or AlNO 3.
Preferably, the Co concentration of the Co and Al containing metal solution is in the range of 90-130g/L, such as 90g/L, 95g/L, 100g/L, 105g/L, 110g/L, 115g/L, 120g/L, 125g/L, 130g/L, etc.
Preferably, the Al concentration of the Co and Al containing metal solution is 1-2g/L, such as 1g/L, 1.2g/L, 1.4g/L, 1.6g/L, 1.8g/L, 2g/L, etc.
Preferably, the alkaline solution is a carbonate and/or bicarbonate containing salt solution, preferably an ammonium bicarbonate solution.
Preferably, the concentration of the alkaline solution is 220-260g/L, such as 220g/L, 225g/L, 230g/L, 235g/L, 240g/L, 245g/L, 250g/L, 255g/L, 260g/L, etc.
Preferably, the base solution has a concentration of 0-50g/L and is free of 0g/L, e.g., 5g/L, 10g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, 50g/L, etc.
Preferably, after step (a) is performed, the Al concentration of the first coating liquid is 0.2-1g/L, e.g. 0.2g/L, 0.4g/L, 0.6g/L, 0.8g/L or 1g/L, etc.
Preferably, after step (b) is performed, the Al concentration of the mixed coating solution is 0.2-1g/L, e.g. 0.2g/L, 0.4g/L, 0.6g/L, 0.8g/L or 1g/L, etc.
In the present invention, if the content of Al element in the coating liquid is too small, the modifying effect on the material is weakened, and if the content is too large, the segregation preventing effect is not achieved.
Preferably, the temperature of the coprecipitation reaction is 35-55 ℃, for example 35 ℃, 40 ℃, 45 ℃, 50 ℃, or 55 ℃, etc.
Preferably, the pH of the coprecipitation reaction is 7.2-7.6, e.g. 7.2, 7.3, 7.4, 7.5 or 7.6, etc.
Preferably, the coprecipitation reaction is carried out under stirring conditions at a rotational speed of 100-300r/min, for example 100r/min, 150r/min, 200r/min, 250r/min or 300r/min, etc.
Preferably, the temperature at which the reaction is continued is 40-55 ℃, e.g., 40 ℃, 45 ℃, 50 ℃, 55 ℃, etc.
Preferably, the pH of the continued reaction is 7.2-7.6, e.g. 7.2, 7.3, 7.4, 7.5 or 7.6, etc.
In a third aspect, the present invention provides a cobalt oxide material obtainable by calcination of cobalt carbonate as described in the first aspect.
Preferably, the cobalt oxide material comprises a cobalt oxide inner core and a cobalt oxide coating layer positioned on the surface of the cobalt oxide inner core, wherein Al and other doping elements in the cobalt oxide coating layer are distributed in a gradient manner.
In the invention, the surface coating layer element and the matrix element are mutually diffused after calcination to form surface gradient coating, thereby realizing the diversification of the surface coating layer function, not only effectively avoiding the problems of surface segregation, morphology cracking and the like, but also accelerating the Li transmission speed of the anode material, relieving the corrosion of electrolyte and improving the cycle and multiplying power performance.
Preferably, the coating is a full coating.
In the invention, the coating mode is full coating, so that particle cracking and Al segregation can be prevented.
Preferably, the preparation method of the cobalt oxide material comprises the following steps: and (3) preparing cobalt carbonate by adopting the method of the second aspect, and calcining after ageing to obtain cobalt oxide.
In the invention, the aging is to stand for a period of time, so that the particle size of the calcined cobalt oxide is more uniform.
Preferably, the aging time is 1-2 hours, such as 1 hour, 1.5 hours, 2 hours, etc.
Preferably, the temperature of the calcination is 500-800 ℃, e.g., 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃, etc.
Preferably, the calcination is for a period of time ranging from 1 to 4 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, etc.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) Mixing cobalt salt solution and Al salt solution to prepare solution A with Co concentration of 90-130g/L and Al concentration of 1-2 g/L; preparing an alkaline solution B with the concentration of 220-260 g/L; preparing a solution C containing any one or at least two of cobalt salt solution, al and Mn, ni, mg, zr or La, wherein the concentration of Al is 0.2-1g/L; preparing a base solution of the reaction container, wherein the concentration of the base solution is 0-50g/L, and the base solution does not contain 0g/L;
(2) Adding a base solution into a reaction container, adding a solution A and a solution B in a parallel flow mode, and performing coprecipitation reaction under the conditions of 35-55 ℃ and pH of 7.2-7.6;
(3) When the cobalt carbonate particles grow to be close to the preset particle size, changing the solution A into the solution C, and continuing to react to obtain cobalt carbonate;
(4) And aging the obtained cobalt carbonate particles for 1-2h, and calcining at 500-800 ℃ for 1-4h to obtain cobalt oxide.
In a fourth aspect, the present invention provides a lithium ion battery, wherein the positive electrode of the lithium ion battery comprises the cobalt oxide in the third aspect.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the following beneficial effects:
The invention provides a cobalt carbonate precursor with a cobalt carbonate coating layer, which takes cobalt carbonate as a matrix, and the surface of the cobalt carbonate precursor is the cobalt carbonate coating layer containing a first doping element. After calcination, the elements of the cobalt oxide surface coating layer and the matrix elements can mutually diffuse to form a multifunctional surface gradient coating layer, so that not only is the aluminum segregation on the particle surface effectively inhibited, the cracking of the particles during calcination prevented, the surface morphology is improved, but also the positive electrode material is effectively prevented from being corroded by electrolyte, the Li transmission speed of the positive electrode material is accelerated, and the cycle and the multiplying power performance of the battery are improved.
Drawings
Fig. 1 is a schematic structural diagram of a cobalt carbonate precursor provided in embodiment 1 of the present invention.
Fig. 2 is a scan of coated modified cobalt carbonate particles provided in example 1 of the present invention, at 10000 x magnification.
Fig. 3 is a scan of coated modified cobalt oxide particles provided in example 1 of the present invention, at 10000 x magnification.
Wherein, 1-cobalt carbonate matrix; 2-cobalt carbonate coating.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a cobalt carbonate, as shown in fig. 1, the cobalt carbonate comprises a cobalt carbonate substrate 1 and a cobalt carbonate coating layer 2 coated on the surface of the cobalt carbonate substrate 1, the cobalt carbonate coating layer 2 contains elements Al and Mn, and the cobalt carbonate substrate 1 contains element Al. The content of Al element in the cobalt carbonate coating layer 2 was 4200ppm, the content of Mn element was 9800ppm, and the content of Al element in the cobalt carbonate matrix 1 was 14000ppm, wherein the content of Al element in the cobalt carbonate coating layer 2 was 30% of the content of Al element in the cobalt carbonate matrix 1, and the content of Mn element was 70% of the content of Al element in the cobalt carbonate matrix 1.
The embodiment also provides a preparation method of the cobalt carbonate and the cobalt oxide obtained by calcination, which specifically comprises the following steps:
(1) Mixing the CoCl 2 solution and the Al 2(SO4)3 solution to prepare a solution A with Co concentration of 90g/L and Al concentration of 1.35 g/L; preparing ammonium bicarbonate solution B with the concentration of 220 g/L; preparing a first coating liquid C containing CoCl 2, al element and Mn element, wherein the Al concentration of the first coating liquid C is 0.6g/L; preparing a base solution ammonium bicarbonate solution of a reaction container, wherein the concentration is 15g/L;
(2) Adding a base solution into a reaction container, adding a solution A and a solution B in a parallel flow mode, and performing coprecipitation reaction at 45 ℃ and pH of 7.4 at a rotating speed of 150r/min;
(3) When the cobalt carbonate particles grow to 15 mu m, the solution A is replaced by the first coating solution C, the reaction temperature is adjusted to 50 ℃, the pH is adjusted to 7.4, and the reaction is continued to obtain the cobalt carbonate precursor with the particle size of 16.5 mu m, wherein the thickness of the cobalt carbonate coating layer is 1.5 mu m.
Fig. 2 is a scanned graph of the coated modified cobalt carbonate particles provided in example 1 of the present invention, and it can be seen from the graph that the coating layer of cobalt carbonate is dense and uniform after coating modification, and thus, all coating is achieved.
The embodiment also provides a cobalt oxide prepared by calcining the cobalt carbonate as a precursor, and the preparation method comprises the following steps:
the obtained cobalt carbonate particles were aged for 1.5 hours and calcined at 650 ℃ for 2.5 hours to obtain cobalt oxide.
Fig. 3 is a scan of the coated and modified cobalt oxide particles provided in example 1 of the present invention, and it can be seen from the graph that the surface of the cobalt oxide particles is dense, the crystal form is uniform and has no cracking, and the coating effect is good after the coating and modification.
Example 2
The embodiment provides a cobalt carbonate, which comprises a cobalt carbonate substrate and a cobalt carbonate coating layer coated on the surface of the cobalt carbonate substrate, wherein the cobalt carbonate coating layer contains elements Al and Mn, and the cobalt carbonate substrate contains the elements Al. The content of Al element in the cobalt carbonate coating layer was 4000ppm, the content of Mn element was 4000ppm, the content of Al element in the cobalt carbonate matrix was 8000ppm, wherein the content of Al element in the cobalt carbonate coating layer was 50% of the content of Al element in the cobalt carbonate matrix, and the content of Mn element was 50% of the content of Al element in the cobalt carbonate matrix.
The embodiment also provides a preparation method of the cobalt carbonate and the cobalt oxide obtained by calcination, which specifically comprises the following steps:
(1) Mixing the CoSO 4 solution and the Al 2NO3 solution to prepare a solution A with Co concentration of 110g/L and Al concentration of 1.5 g/L; preparing ammonium bicarbonate solution B with the concentration of 240 g/L; preparing a first coating liquid C containing CoSO 4, al element and Mn element, wherein the concentration is 0.3g/L; preparing a base solution ammonium bicarbonate solution of a reaction container, wherein the concentration is 25g/L;
(2) Adding a base solution into a reaction container, adding a solution A and a solution B in a parallel flow mode, and performing coprecipitation reaction at 35 ℃ and pH of 7.2 at the rotating speed of 100r/min;
(3) When the cobalt carbonate particles grow to 16 mu m, the solution A is replaced by the first coating solution C, the reaction temperature is adjusted to 40 ℃, the pH is adjusted to 7.2, and the reaction is continued to obtain the cobalt carbonate precursor with the particle size of 17 mu m, wherein the thickness of the cobalt carbonate coating layer is 1 mu m.
The embodiment also provides a cobalt oxide prepared by calcining the cobalt carbonate as a precursor, and the preparation method comprises the following steps:
the obtained cobalt carbonate particles were aged for 1 hour and calcined at 500 ℃ for 4 hours to obtain cobalt oxide.
Example 3
The embodiment provides a cobalt carbonate, which comprises a cobalt carbonate substrate and a cobalt carbonate coating layer coated on the surface of the cobalt carbonate substrate, wherein the cobalt carbonate coating layer contains elements Al, mn and Ni, and the cobalt carbonate substrate contains the element Al. The content of Al element in the cobalt carbonate coating layer was 2000ppm, the content of Mn element was 10000ppm, the content of Ni element was 8000ppm, and the content of Al element in the cobalt carbonate matrix was 20000ppm, wherein the content of Al element in the cobalt carbonate coating layer was 10% of the content of Al element in the cobalt carbonate matrix, and the sum of the content of Mn and Ni elements was 90% of the content of Al element in the cobalt carbonate matrix.
The embodiment also provides a preparation method of the cobalt carbonate and the cobalt oxide obtained by calcination, which specifically comprises the following steps:
(1) Mixing CoNO 3 solution and AlCl 3 solution to prepare solution A with Co concentration of 130g/L and Al concentration of 2 g/L; preparing ammonium bicarbonate solution B with the concentration of 260 g/L; preparing a first coating liquid C containing CoNO 3, al element, mn element and Ni element, wherein the concentration is 1g/L; preparing a base solution ammonium bicarbonate solution of a reaction container, wherein the concentration is 50g/L;
(2) Adding a base solution into a reaction container, adding a solution A and a solution B in a parallel flow mode, and performing coprecipitation reaction at 55 ℃ and pH of 7.6 at the rotating speed of 300r/min;
(3) When the cobalt carbonate particles grow to 18 mu m, the solution A is replaced by the first coating solution C, the reaction temperature is adjusted to 40 ℃, the pH is adjusted to 7.2, and the reaction is continued to obtain a cobalt carbonate precursor with the particle size of 20 mu m, wherein the thickness of the cobalt carbonate coating layer is 2 mu m.
The embodiment also provides a cobalt oxide prepared by calcining the cobalt carbonate as a precursor, and the preparation method comprises the following steps:
the obtained cobalt carbonate particles were aged for 2 hours and calcined at 800 ℃ for 1 hour to obtain cobalt oxide.
Example 4
The difference between this example and example 1 is that the content of Al element in the cobalt carbonate coating layer was 1120ppm, that is, 8% of the content of Al element in the cobalt carbonate matrix.
The remaining preparation methods and parameters remain the same as in example 1.
Example 5
The difference between this example and example 1 is that the content of Al element in the cobalt carbonate coating layer was 7700ppm, that is, 55% of the content of Al element in the cobalt carbonate matrix.
The remaining preparation methods and parameters remain the same as in example 1.
Example 6
The difference between this example and example 1 is that the content of Mn element in the cobalt carbonate coating layer was 5600ppm, that is, 40% of the content of Al element in the cobalt carbonate matrix.
The remaining preparation methods and parameters remain the same as in example 1.
Example 7
The difference between this example and example 1 is that the content of Mn element in the cobalt carbonate coating layer was 13300ppm, that is, 95% of the content of Al element in the cobalt carbonate matrix.
The remaining preparation methods and parameters remain the same as in example 1.
Example 8
The difference between this example and example 1 is that the thickness of the cobalt carbonate coating layer obtained in step (3) was 0.5. Mu.m
The remaining preparation methods and parameters remain the same as in example 1.
Example 9
The difference between this example and example 1 is that the thickness of the cobalt carbonate coating layer obtained in step (3) was 2.5. Mu.m
The remaining preparation methods and parameters remain the same as in example 1.
Comparative example 1
This comparative example is different from example 1 in that a first coating liquid C containing Al element and Mn element without CoCl 2 is prepared in step (1).
The remaining preparation methods and parameters remain the same as in example 1.
Comparative example 2
This comparative example is different from example 1 in that a first coating liquid C containing CoCl 2 and Al element was prepared in step (1).
The remaining preparation methods and parameters remain the same as in example 1.
Performance test:
preparing a positive electrode active material by using cobalt oxide prepared in the examples 1-9 and the comparative examples 1-2 as a precursor, and assembling the positive electrode active material into a lithium ion battery, wherein the preparation method of the positive electrode comprises the steps of mixing the cobalt oxide precursor and lithium salt in proportion, calcining at 800 ℃ for 24 hours, preparing the positive electrode active material, uniformly mixing the active material, a conductive agent and a binder according to the proportion of 75:15:10, smearing the mixture on a cut aluminum foil, and drying in a vacuum drying oven to obtain a positive electrode plate;
The negative electrode is a lithium sheet;
The composition of the electrolyte is as follows: 1mol/L LiPF 6 solution, wherein the solvent is a mixed solvent of DMC, EC, DEC and EMC according to the volume ratio of 1:1:1:1;
Diaphragm model: celgard 2400;
specific capacity test: the specific capacity is tested under the voltage window of 2-4.5V after 0.1C charge and 0.1C discharge, and the specific capacity of discharge is recorded;
Testing the cycle performance: testing the cycle performance under the conditions of 0.1C charge, 0.2C discharge and voltage window of 2-4.5V;
Testing rate performance: the rate performance was tested at 0.5C charge, 1C discharge, voltage window 2-4.5V, and specific discharge capacity was recorded.
TABLE 1
Analysis:
The data in examples 1-9 show that the Al segregation on the surface of the particles is inhibited and the surface morphology of the particles is improved after the particles are coated by a cobalt carbonate coating layer containing Al and other doping elements, and the performance of the prepared lithium ion battery is also obviously improved.
As is clear from comparison of the data results of examples 1 and 5, when the content of Al element in the cobalt carbonate coating layer is too low, the modifying effect on the material is weakened, and thus the specific capacity and the cycle stability of the battery are lowered, and the rate performance is also poor, whereas when the content of Al element in the cobalt carbonate coating layer is too high, the function of suppressing Al segregation is weakened, resulting in a significant lowering of the rate performance of the battery.
As can be seen from comparison of the data results of examples 1 and 6 and 7, the content of other doping elements in the cobalt carbonate coating layer is too small, which results in a decrease in stability of the battery, a decrease in rate performance, and the content of other doping elements in the cobalt carbonate coating layer is too large, which results in a decrease in specific capacity of the material and a decrease in cycling stability of the battery.
As is clear from comparison of the data results of examples 1 and 9, when the thickness of the cobalt carbonate coating layer is too thin, the calcination process is liable to fall off, and thus segregation is not effectively suppressed and cracking problems are solved, so that the specific capacity of the material and the cycle stability and rate performance of the battery are reduced, and when the thickness of the cobalt carbonate coating layer is too thick, the electrochemical performance of the body is affected, resulting in a reduction in the specific capacity of the material and a reduction in the cycle stability and rate performance of the battery.
As is clear from comparison of the data results of example 1 and comparative example 1, when the coating layer is a coating layer of Al and other doping elements and does not contain cobalt carbonate, not only the Al segregation on the particle surface cannot be effectively suppressed, the surface morphology is improved, but also the specific capacity of the material is significantly reduced, and the cycle stability and the rate performance of the battery are also significantly reduced.
As is clear from comparison of the data results of example 1 and comparative example 2, the cobalt carbonate coating layer does not contain doping elements other than Al, so that the multifunction of the surface coating layer cannot be realized, the specific capacity of the material is remarkably reduced, and the cycle stability and the rate performance of the battery are remarkably reduced.
In conclusion, the segregation of the Al is inhibited after coating, the specific capacity of the material is obviously improved, and meanwhile, the cycle performance is also greatly improved, so that the coating layer is proved to be stable and not easy to fall off, and the conditions of structural collapse and the like of the positive electrode material can be effectively prevented; the improvement effect of the multiplying power performance is obvious, which shows that the coating layer can provide a rapid lithium ion transmission channel and serve as a lithium ion transmission transfer station, thereby optimizing the multiplying power performance of the material.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (34)
1. The cobalt carbonate is characterized by comprising an Al-doped cobalt carbonate matrix and a cobalt carbonate coating layer coated on the surface of the Al-doped cobalt carbonate matrix, wherein the cobalt carbonate coating layer contains Al and other doping elements;
the other doping elements in the cobalt carbonate coating layer comprise any one or a combination of at least two of Mn, ni, mg, zr and La;
the cobalt carbonate is prepared by adopting the following method, and the preparation method comprises the following steps:
Co-precipitation reaction is carried out on metal solution containing Co and Al and alkaline solution to prepare cobalt carbonate, when cobalt carbonate particles grow to be close to a preset particle size, any operation of (a) or (b) is carried out, and then the reaction is continued to obtain cobalt carbonate,
(A) Changing the metal solution into a first coating liquid, wherein the components of the first coating liquid comprise: cobalt salt solution, al and other doping elements;
(b) Replacing part of the metal solution to obtain a mixed coating solution, wherein the components of the second coating solution comprise Al and other doping elements;
the near-preset particle size is: the difference between the preset particle size and the actual particle size is 1-2 μm.
2. The cobalt carbonate according to claim 1, wherein the Al doping amount in the Al doped cobalt carbonate matrix is 8000ppm to 20000ppm.
3. The cobalt carbonate according to claim 1, wherein the content of Al in the cobalt carbonate coating layer is 10 to 50% of the Al doping amount in the Al-doped cobalt carbonate matrix, based on 100% of the mass of the cobalt carbonate coating layer.
4. The cobalt carbonate according to claim 1, wherein the content of the other doping element in the cobalt carbonate coating layer is a difference between the Al doping amount in the cobalt carbonate substrate and the Al content in the cobalt carbonate coating layer, based on 100% by mass of the cobalt carbonate substrate.
5. The cobalt carbonate according to claim 1, wherein the content of other doping elements in the cobalt carbonate cladding layer is 50% -90% of the Al doping amount in the Al doped cobalt carbonate matrix.
6. The cobalt carbonate according to claim 1, wherein the content of other doping elements in the cobalt carbonate matrix is less than 0.05% based on 100% of the mass of the Al-doped cobalt carbonate matrix.
7. The cobalt carbonate according to claim 1, wherein the cobalt carbonate coating has a thickness of 1-2 μm.
8. A process for the preparation of cobalt carbonate according to any one of claims 1 to 7, comprising:
Co-precipitation reaction is carried out on metal solution containing Co and Al and alkaline solution to prepare cobalt carbonate, when cobalt carbonate particles grow to be close to a preset particle size, any operation of (a) or (b) is carried out, and then the reaction is continued to obtain cobalt carbonate,
(A) Changing the metal solution into a first coating liquid, wherein the components of the first coating liquid comprise: cobalt salt solution, al and other doping elements;
(b) Replacing part of the metal solution to obtain a mixed coating solution, wherein the components of the second coating solution comprise Al and other doping elements;
the near-preset particle size is: the difference between the preset particle size and the actual particle size is 1-2 μm.
9. The method of preparing cobalt carbonate according to claim 8, wherein the Co-precipitation reaction of the metal solution containing Co and Al with the alkaline solution comprises the steps of:
(1) Preparing a metal solution, an alkaline solution and a base solution containing Co and Al respectively;
(2) Adding a base solution into a reaction vessel, adding a metal solution containing Co and Al and an alkaline solution in a parallel flow mode, and performing coprecipitation reaction.
10. The method of claim 9, wherein the Co and Al-containing metal solution comprises a Co-containing compound and an Al-containing compound.
11. The method of claim 10, wherein the Co-containing compound comprises any one or a combination of at least two of CoCl 2、CoSO4 or CoNO 3.
12. The method of claim 10, wherein the Al-containing compound comprises any one of AlCl 3、Al2(SO4)3 or Al (NO 3)3) or a combination of at least two.
13. The method according to claim 9, wherein the Co concentration of the Co and Al-containing metal solution is 90-130g/L.
14. The method according to claim 9, wherein the Al concentration of the Co and Al-containing metal solution is 1-2g/L.
15. The method according to claim 9, wherein the alkaline solution is a carbonate and/or bicarbonate-containing salt solution.
16. The method of claim 15, wherein the alkaline solution is an ammonium bicarbonate solution.
17. The method according to claim 9, wherein the concentration of the alkaline solution is 220-260g/L.
18. The method according to claim 9, wherein the concentration of the base liquid is 0 to 50g/L and 0g/L is not contained.
19. The method according to claim 8, wherein the Al concentration of the first coating liquid after the step (a) is 0.2 to 1g/L.
20. The method according to claim 8, wherein the Al concentration of the mixed coating liquid is 0.2-1g/L after the step (b) is performed.
21. The method of claim 8, wherein the temperature of the coprecipitation reaction is 35-55 ℃.
22. The method of claim 8, wherein the pH of the coprecipitation reaction is 7.2 to 7.6.
23. The method according to claim 8, wherein the coprecipitation reaction is carried out under stirring at a rotation speed of 100 to 300r/min.
24. The process of claim 8, wherein the temperature at which the reaction is continued is from 40 ℃ to 55 ℃.
25. The method of claim 8, wherein the pH of the continued reaction is 7.2-7.6.
26. A cobalt oxide material, characterized in that it is obtained by calcination of the cobalt carbonate according to any one of claims 1-7.
27. The cobalt oxide material of claim 26, wherein the cobalt oxide material comprises a cobalt oxide core and a cobalt oxide cladding layer on a surface of the cobalt oxide core, wherein Al and other doping elements in the cobalt oxide cladding layer are distributed in a gradient.
28. The cobalt oxide material of claim 27, wherein the cladding in the cladding layer is a total cladding.
29. A method of preparing a cobalt oxide material according to any one of claims 26 to 28, wherein the method of preparing a cobalt oxide material comprises:
The method of any one of claims 8-25, wherein the cobalt carbonate is prepared by aging and calcining.
30. The method of claim 29, wherein the aging is for a period of 1 to 2 hours.
31. The method of claim 29, wherein the calcination temperature is 500-800 ℃.
32. The method of claim 29, wherein the calcination is for a period of 1 to 4 hours.
33. The method of preparation of claim 29, comprising the steps of:
(1) Mixing cobalt salt solution and Al salt solution to prepare solution A with Co concentration of 90-130g/L and Al concentration of 1-2 g/L; preparing an alkaline solution B with the concentration of 220-260 g/L; preparing a solution C containing any one or at least two of cobalt salt solution, al and Mn, ni, mg, zr or La, wherein the concentration of Al is 0.2-1g/L; preparing a base solution of the reaction container, wherein the concentration of the base solution is 0-50g/L, and the base solution does not contain 0g/L;
(2) Adding a base solution into a reaction container, adding a solution A and a solution B in a parallel flow mode, and performing coprecipitation reaction under the conditions of 35-55 ℃ and pH of 7.2-7.6;
(3) When the cobalt carbonate particles grow to be close to the preset particle size, changing the solution A into the solution C, and continuing to react to obtain cobalt carbonate;
(4) And aging the obtained cobalt carbonate particles for 1-2h, and calcining at 500-800 ℃ for 1-4h to obtain cobalt oxide.
34. A lithium ion battery comprising a cobalt oxide material according to any one of claims 26 to 28 in a positive electrode.
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