CN115893512A - Doped cobalt carbonate and preparation method and application thereof - Google Patents
Doped cobalt carbonate and preparation method and application thereof Download PDFInfo
- Publication number
- CN115893512A CN115893512A CN202211471456.7A CN202211471456A CN115893512A CN 115893512 A CN115893512 A CN 115893512A CN 202211471456 A CN202211471456 A CN 202211471456A CN 115893512 A CN115893512 A CN 115893512A
- Authority
- CN
- China
- Prior art keywords
- solution
- yttrium
- cobalt
- carbonate
- doped
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910021446 cobalt carbonate Inorganic materials 0.000 title claims abstract description 54
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 72
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 64
- 239000010452 phosphate Substances 0.000 claims abstract description 64
- 239000000243 solution Substances 0.000 claims description 79
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 26
- VQVNCTNULYBZGL-UHFFFAOYSA-N cobalt yttrium Chemical compound [Co].[Y] VQVNCTNULYBZGL-UHFFFAOYSA-N 0.000 claims description 24
- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- 239000010941 cobalt Substances 0.000 claims description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 18
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 238000000975 co-precipitation Methods 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- 239000012716 precipitator Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 11
- -1 yttrium ions Chemical class 0.000 abstract description 8
- 230000005540 biological transmission Effects 0.000 abstract description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 description 11
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 9
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 9
- 239000007774 positive electrode material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
Abstract
The invention discloses doped cobalt carbonate and a preparation method and application thereof. The doped cobalt carbonate is yttrium and phosphate radical double-ion doped cobalt carbonate. According to the invention, cobalt carbonate is codoped by doping elements yttrium (Y) and phosphate radicals, yttrium has a larger ionic radius, so that a lithium ion transmission channel can be enlarged, and the structure of the material is well stabilized. The doping of yttrium ions and phosphate radicals can improve the thermal stability and the ion transmission rate of the material.
Description
Technical Field
The invention relates to the technical field of new energy, and relates to doped cobalt carbonate and a preparation method and application thereof.
Background
The lithium cobaltate anode material is widely applied to the field of 3C digital electronics, the specific capacity of a conventional voltage window is only about 140mAh/g and is far lower than the theoretical specific capacity, the capacity can be effectively increased by increasing the upper limit of the voltage, but the problems of unstable structure, easy collapse, poor cycle performance and the like can be caused.
In order to improve the specific capacity of the material, the material structure is stabilized by doping Al, and the common doping method is to dope the material structure during preparation of a precursor cobalt oxide, so that the upper limit voltage of charge is increased to increase the capacity. However, as the amount of doped Al increases, al segregation gradually occurs, and the capacity decreases, which is not a good consideration.
CN109786738A discloses a high-voltage lithium cobalt oxide positive electrode material, a preparation method thereof and a lithium ion battery, wherein the high-voltage lithium cobalt oxide positive electrode material comprises lithium position substitution doped lithium cobalt oxide, and the general formula of the lithium position substitution doped lithium cobalt oxide is Li 1-x Ma x CoO 2 (ii) a Wherein x is more than 0 and less than or equal to 0.05, the Ma is a doping element and is selected from one or more elements with the ionic radius range of 68 pm-90 pm and the ionic valence state of more than or equal to 1. According to the high-voltage lithium cobalt oxide positive electrode material, the lithium position of lithium cobalt oxide is subjected to substitution doping, so that the electrostatic interaction and cobalt dissolution of the lithium cobalt oxide caused by lithium falling out under high voltage are relieved, the structure and the cycling stability of the material are improved, and the material has high capacity and good cycling stability under high voltage. However, the incorporation mechanism is uncertain, and the incorporation position is unclear, and the method belongs to the theoretical category.
CN105591081A discloses a high-voltage high-rate lithium cobaltate positive electrode material and a preparation method thereof, wherein cobalt oxide and lithium carbonate are adopted as precursors, magnesium carbonate is added, and lithium cobaltate can be obtained after primary sintering and crushing; and then adding a mixed alcohol solution of aluminum alkoxide and titanate, mixing, and then sintering for the second time to obtain the lithium cobaltate. When the discharge voltage of the lithium cobaltate prepared by the method is cut off to 4.5V, the specific capacity at 0.2C multiplying power is higher than 190mAh/g, the multiplying power performance of 1C/0.2C exceeds 98%, and the platform occupancy rate of 3.6V is more than 99%; the lithium cobalt oxide positive electrode material has the characteristics of stable structure and small discharge specific capacity attenuation in the high-voltage high-rate charge and discharge process, and improves the voltage window, capacity performance and rate performance of the lithium cobalt oxide positive electrode material. However, the doped Al and Mg belong to solid phase doping, the doping amount is small, the doping is not uniform, repeated calcination is needed, and the process is complex.
Therefore, it is necessary to provide a simple method for preparing high-performance high-voltage cobalt oxide, which is beneficial to popularization and application.
Disclosure of Invention
The invention aims to provide doped cobalt carbonate and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a doped cobalt carbonate, wherein the doped cobalt carbonate is yttrium and phosphate radical double ion doped cobalt carbonate.
According to the invention, cobalt carbonate is codoped by doping yttrium (Y) and phosphate radicals, wherein yttrium has a larger ionic radius, so that a lithium ion transmission channel can be enlarged, and the structure of the material is well stabilized. The doping of yttrium ions and phosphate radicals can improve the thermal stability and the ion transmission rate of the material.
Preferably, the doping amount of yttrium element is 0.2-1%, for example 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, etc., based on the total mass of the doped cobalt carbonate.
The invention selects yttrium with larger ionic radius for doping, so that the doping amount is less, and the loss of the capacity of the active material of the body can not be caused.
Preferably, the doping amount of the phosphate radical is 0.2-1%, for example, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, or the like, based on the total mass of the doped cobalt carbonate. If the doping amount of phosphate is too small, the ion transport efficiency is not significantly improved.
In a second aspect, the present invention provides a method for preparing doped cobalt carbonate according to the first aspect, comprising the following steps:
(1) Respectively preparing a metal solution, a precipitator solution and a base solution;
the metal solution is a cobalt yttrium mixed solution, or the metal solution is a cobalt solution and an yttrium solution which exist independently;
the precipitating agent comprises a first precipitating agent comprising a carbonate and/or bicarbonate and a second precipitating agent comprising a phosphate;
(2) And adding the metal solution and the precipitant solution into the base solution to perform coprecipitation reaction to obtain the doped cobalt carbonate.
According to the method, yttrium ions are introduced into a cobalt-containing metal solution, phosphate radicals are introduced into a precipitator, coprecipitation reaction is carried out, co-doping of the yttrium ions and the phosphate radicals can be achieved, and compared with doping carried out in a later lithium-matched calcining stage, doping carried out in the coprecipitation stage is more uniform.
Preferably, the preparation method of the cobalt-yttrium mixed solution comprises the following steps: dispersing a cobalt source and an yttrium source into water to obtain the cobalt-yttrium mixed solution;
preferably, the preparation method of the cobalt solution comprises the following steps: dispersing a cobalt source into water to obtain the cobalt solution;
preferably, the preparation method of the yttrium solution comprises the following steps: dispersing an yttrium source into water to obtain an yttrium solution;
preferably, the cobalt yttrium mixed solution and the cobalt source in the cobalt solution independently comprise CoCl 2 、CoSO 4 And Co (NO) 3 ) 2 At least one of (a).
Preferably, the yttrium sources in the cobalt yttrium mixed solution and the yttrium solution independently comprise YCl 3 。
Preferably, the concentration of the cobalt element in the cobalt source is 90-130g/L, such as 90g/L, 95g/L, 100g/L, 105g/L, 110g/L, 115g/L, 120g/L, 130g/L, etc., based on the total amount of the metal solution.
Preferably, the concentration of yttrium element in the yttrium source is 0.1-0.5g/L, such as 0.1g/L, 0.2g/L, 0.3g/L, 0.4g/L, or 0.5g/L, etc., based on the total amount of the metal solution.
Preferably, the carbonate comprises Na 2 CO 3 And (NH) 4 ) 2 CO 3 At least one of (1).
Preferably, the bicarbonate comprises NH 4 HCO 3 And NaHCO 3 At least one of (1).
Preferably, the concentration of the first precipitant in the precipitant solution is 200-260g/L, such as 200g/L, 205g/L, 210g/L, 220g/L, 225g/L, 230g/L, 240g/L, 250g/L, or 260g/L, and the like.
Preferably, the phosphate comprises NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 And (NH) 4 ) 3 PO 4 At least one of (1).
Preferably, the concentration of phosphate in the precipitant solution is 2-5g/L, such as 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L, or 5g/L, and the like.
Preferably, the ratio of the flow rates of the metal solution and the precipitant solution is 1 (1-2), such as 1.
Preferably, the base solution is a mixed solution of carbonate and phosphate, or the base solution is water.
Preferably, the carbonate concentration in the base solution is 0-50g/L, such as 0g/L, 2g/L, 5g/L, 8g/L, 10g/L, 12g/L, 15g/L, 20g/L, 25g/L, 30g/L, 35g/L, 40g/L, 45g/L, or 50g/L, etc., and the phosphate concentration is 0-1g/L, such as 0g/L, 0.2g/L, 0.5g/L, 0.8g/L, 1g/L, etc.
In one embodiment, the base solution is placed in a reaction kettle, and the metal solution and the precipitant solution are pumped into the reaction kettle simultaneously at a certain pH and temperature to perform coprecipitation reaction.
Preferably, the temperature of the co-precipitation reaction is 40-60 ℃, such as 40 ℃, 45 ℃, 50 ℃, 55 ℃ or 60 ℃ and the like.
Preferably, the pH of the co-precipitation reaction is 7.0-7.6, such as 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, or 7.6, and the like.
In one embodiment, after the coprecipitation reaction is carried out to a stopped reactor particle size (i.e., a target particle size), the coprecipitated product is washed and dried.
In a third aspect, the present invention provides a doped cobalt oxide, wherein the doped cobalt oxide is prepared by calcining the doped cobalt carbonate described in the first aspect.
Preferably, the temperature of the calcination is 500-800 ℃, such as 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃ and the like.
In a fourth aspect, the present invention provides a lithium cobaltate, which is prepared by using the doped cobalt oxide according to the third aspect.
In a fifth aspect, the invention provides a battery, wherein a positive electrode of the battery comprises the doped cobalt carbonate of the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, cobalt carbonate is codoped by doping elements yttrium (Y) and phosphate radicals, yttrium has a larger ionic radius, so that a lithium ion transmission channel can be enlarged, and the structure of the material is well stabilized. The doping of yttrium ions and phosphate radicals can improve the thermal stability and the ion transmission rate of the material.
(2) According to the method, yttrium ions are introduced into the cobalt-containing metal solution, phosphate radicals are introduced into the precipitator, and coprecipitation reaction is carried out, so that more uniform co-doping of the yttrium ions and the phosphate radicals can be realized.
(3) The method is simple, has good matching property with the existing coprecipitation reaction equipment, can obtain the high-performance doped cobalt carbonate only by adjusting the raw materials, and is suitable for industrial production.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The present example provides an yttrium and phosphate double-doped cobalt carbonate, wherein the doping amount of an yttrium element is 0.2% and the doping amount of a phosphate is 0.2% based on the total mass of the yttrium and phosphate double-doped cobalt carbonate.
The preparation method of the yttrium and phosphate radical double-doped cobalt carbonate comprises the following steps:
step one, preparing a cobalt-yttrium mixed solution A:
adding CoCl 2 、YCl 3 Mixing with water to obtain a cobalt-yttrium mixed solution A with the Co concentration of 90g/L and the Y concentration of 0.3 g/L;
preparing a precipitant solution B:
reacting NH 4 HCO 3 、NH 4 H 2 PO 3 Mixing with water to obtain NH 4 HCO 3 The precipitant solution B with the concentration of 220g/L and the phosphate radical concentration of 3.5 g/L.
And step two, adding pure water as a base solution into a reaction kettle, and pumping the cobalt-yttrium mixed solution A and the precipitant solution B into the reaction kettle at the same time according to a flow ratio of 1.
And step three, after the reaction reaches the grain diameter of the reactor, washing and drying to obtain yttrium and phosphate radical double-doped cobalt carbonate.
The embodiment also provides cobalt oxide prepared by using the yttrium and phosphate double-doped cobalt carbonate, and the preparation method comprises the following steps:
calcining the yttrium and phosphate radical double-doped cobalt carbonate at 720 ℃ to obtain the cobalt oxide.
Example 2
The embodiment provides yttrium and phosphate radical double-doped cobalt carbonate, wherein the doping amount of yttrium element is 0.5% and the doping amount of phosphate radical is 0.3% based on the total mass of the yttrium and phosphate radical double-doped cobalt carbonate.
The preparation method of the yttrium and phosphate radical double-doped cobalt carbonate comprises the following steps:
step one, preparing a cobalt-yttrium mixed solution A:
adding CoSO 4 、YCl 3 Mixing with water to obtain a cobalt-yttrium mixed solution A with the Co concentration of 110g/L and the Y concentration of 0.2 g/L;
preparing a precipitant solution B:
reacting NH 4 HCO 3 、(NH 4 ) 2 HPO 4 Mixing with water to obtain NH 4 HCO 3 The precipitant solution B with the concentration of 240g/L and the phosphate radical concentration of 4 g/L.
And step two, adding a mixed solution of 40g/L carbonate and 0.6g/L phosphate into a reaction kettle as a base solution, and pumping the cobalt-yttrium mixed solution A and the precipitator solution B into the reaction kettle at the same time for coprecipitation reaction at a certain pH and temperature, wherein the pH is 7.2, and the temperature is 50 ℃.
And step three, after the reaction reaches the grain diameter of the reactor, washing and drying to obtain yttrium and phosphate radical double-doped cobalt carbonate.
The embodiment also provides cobalt oxide prepared by using the yttrium and phosphate double-doped cobalt carbonate, and the preparation method comprises the following steps:
calcining the yttrium and phosphate radical double-doped cobalt carbonate at 600 ℃ to obtain the cobalt oxide.
Example 3
The present example provides an yttrium and phosphate double-doped cobalt carbonate, wherein the doping amount of an yttrium element is 0.6% and the doping amount of a phosphate is 0.4% based on the total mass of the yttrium and phosphate double-doped cobalt carbonate.
The preparation method of the yttrium and phosphate radical double-doped cobalt carbonate comprises the following steps:
step one, preparing a cobalt-yttrium mixed solution A:
mixing Co (NO) 3 ) 2 、YCl 3 Mixing with water to obtain a cobalt-yttrium mixed solution A with the Co concentration of 120g/L and the Y concentration of 0.4 g/L;
preparing a precipitant solution B:
reacting NH 4 HCO 3 、(NH 4 ) 3 PO 4 Mixing with water to obtain NH 4 HCO 3 The precipitant solution B with the concentration of 250g/L and the phosphate radical concentration of 2.5 g/L.
Step two, adding 20g/L Na into the reaction kettle 2 CO 3 And 0.2g/L (NH) 4 ) 3 PO 4 Preparing a base solution, and simultaneously pumping the cobalt-yttrium mixed solution A and the precipitator solution B into a reaction kettle for coprecipitation at a certain pH and temperatureReaction, wherein the pH is 7.8 and the temperature is 45 ℃.
And step three, after the reaction reaches the grain diameter of the reactor, washing and drying to obtain yttrium and phosphate radical double-doped cobalt carbonate.
The embodiment also provides cobalt oxide prepared by using the yttrium and phosphate double-doped cobalt carbonate, and the preparation method comprises the following steps:
calcining the yttrium and phosphate radical double-doped cobalt carbonate at 780 ℃ to obtain the cobalt oxide.
Example 4
The embodiment provides yttrium and phosphate radical double-doped cobalt carbonate, wherein the doping amount of yttrium element is 0.5% and the doping amount of phosphate radical is 0.2% based on the total mass of the yttrium and phosphate radical double-doped cobalt carbonate.
The preparation method of the yttrium and phosphate radical double-doped cobalt carbonate comprises the following steps:
step one, preparing a cobalt yttrium mixed solution A:
mixing Co (NO) 3 ) 2 、YCl 3 Mixing with water to obtain a cobalt-yttrium mixed solution A with the Co concentration of 100g/L and the Y concentration of 0.5 g/L;
preparing a precipitant solution B:
will be (NH) 4 ) 2 CO 3 、(NH 4 ) 3 PO 4 Mixing with water to obtain NH 4 HCO 3 The precipitant solution B has a concentration of 230g/L and a phosphate radical concentration of 3 g/L.
Step two, adding 15g/L Na into the reaction kettle 2 CO 3 And 0.15g/L (NH) 4 ) 3 PO 4 And (3) preparing a base solution, and simultaneously pumping the cobalt-yttrium mixed solution A and the precipitator solution B into a reaction kettle for coprecipitation reaction at a certain pH and temperature, wherein the pH is 7.8, and the temperature is 60 ℃.
And step three, after the reaction reaches the grain diameter of the reactor, washing and drying to obtain yttrium and phosphate radical double-doped cobalt carbonate.
The embodiment also provides cobalt oxide prepared by using the yttrium and phosphate double-doped cobalt carbonate, and the preparation method comprises the following steps:
calcining the cobalt carbonate doubly doped with yttrium and phosphate radical at 575 ℃ to obtain the cobalt oxide.
Example 5
The difference from example 1 is that the doping amount of yttrium element is 0.1%.
Example 6
The difference from example 1 is that the doping amount of yttrium element is 2%.
Example 7
The difference from example 1 is that the doping amount of phosphate is 0.1%.
Example 8
The difference from example 1 is that the doping amount of phosphate is 2%.
Example 9
The difference from example 1 is that a cobalt yttrium mixed solution is not prepared, but a cobalt solution and an yttrium solution are separately pumped, and the Co concentration and the Y concentration in this example are the same as those in example 1.
Comparative example 1
The difference from example 1 is that the cobalt yttrium mixed solution is replaced by a cobalt solution, that is, no yttrium element is introduced in the preparation method.
Comparative example 2
The difference from example 1 is that no NH was added during the preparation of the precipitant solution B 4 H 2 PO 3 。
The button cell is assembled by using lithium cobaltate obtained by calcining the cobalt oxide matched with lithium prepared in each embodiment and comparative example as a positive electrode active material, and the specific method comprises the following steps:
preparing a positive electrode: 80wt% of a positive electrode active material, 10wt% of Super-P and 10wt% of polyvinylidene fluoride (PVDF) were dispersed in an N-methylpyrrolidone (NMP) solution to prepare an electrode slurry, which was coated on an aluminum foil and dried to obtain a positive electrode.
Preparing a negative electrode: graphite is used as a negative active material, 80wt% of negative active material, 10wt% of Super-P, 5wt% of SBR and 5wt% of CMC are dispersed in water to prepare electrode slurry, and the electrode slurry is coated on copper foil and dried to obtain a negative electrode.
The electrolyte comprises the following components: 1M LiPF 6 And mixtures of EC, DMC and EMC (EC: DMC: EMC volume ratio = 1.
The button cell is assembled by adopting the anode, the cathode and the electrolyte.
And (3) testing:
and (3) performing electrochemical performance characterization by using the button cell.
And (3) thermal stability characterization: the high temperature cycle performance was tested at 45 ℃ at 0.5C/0.5C for 300 cycles, and the results are shown in Table 1.
And (3) rate characterization: A0.5/2C rate test was performed at 25 ℃ to characterize the difference in lithium ion transmission rate, and the capacity retention was found in Table 1.
TABLE 1
As can be seen from Table 1, the cobalt carbonate is codoped by doping yttrium (Y) and phosphate radicals, so that the high-temperature cycle performance and the rate performance of the battery can be effectively improved.
Meanwhile, as can be seen from the comparison between example 1 and examples 5 to 8, the doping amounts of the element yttrium and the phosphate exist in the preferable range, and the ion transport rate in the preferable range is higher, thereby affecting the electrochemical performance of the battery.
As can be seen from the comparison of example 1 with comparative examples 1 and 2, the doping of the elements yttrium and phosphate is necessary, and none of them leads to the failure of the synergistic improvement of the high-temperature cycle performance and rate capability of the battery.
The applicant states that the present invention is illustrated by the above examples to show the detailed method of the present invention, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be carried out. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The doped cobalt carbonate is characterized in that the doped cobalt carbonate is yttrium and phosphate radical double-ion doped cobalt carbonate.
2. The doped cobalt carbonate according to claim 1, wherein the doping amount of yttrium element is 0.2-1% based on the total mass of the doped cobalt carbonate;
preferably, the doping amount of the phosphate radical is 0.2-1% based on the total mass of the doped cobalt carbonate.
3. A method for preparing doped cobalt carbonate according to claim 1 or 2, characterized in that it comprises the following steps:
(1) Respectively preparing a metal solution, a precipitator solution and a base solution;
the metal solution is a cobalt yttrium mixed solution, or the metal solution is a cobalt solution and an yttrium solution which independently exist;
the precipitating agent comprises a first precipitating agent comprising a carbonate and/or bicarbonate and a second precipitating agent comprising a phosphate;
(2) And adding the metal solution and the precipitant solution into the base solution to perform coprecipitation reaction to obtain the doped cobalt carbonate.
4. The method according to claim 3, wherein the cobalt yttrium mixed solution is prepared by a method comprising: dispersing a cobalt source and an yttrium source into water to obtain the cobalt-yttrium mixed solution;
preferably, the preparation method of the cobalt solution comprises the following steps: dispersing a cobalt source into water to obtain a cobalt solution;
preferably, the preparation method of the yttrium solution comprises the following steps: dispersing an yttrium source into water to obtain an yttrium solution;
preferably, the cobalt source in the cobalt yttrium mixed solution and the cobalt solution independently comprises CoCl 2 、CoSO 4 And Co (NO) 3 ) 2 At least one of;
preferably, the yttrium sources in the cobalt yttrium mixed solution and the yttrium solution independently comprise YCl 3 ；
Preferably, the concentration of the cobalt element in the cobalt source is 90-130g/L based on the total amount of the metal solution;
preferably, the concentration of yttrium element in the yttrium source is 0.1-0.5g/L based on the total amount of the metal solution.
5. The method according to claim 3 or 4, wherein the carbonate comprises Na 2 CO 3 And (NH) 4 ) 2 CO 3 At least one of;
preferably, the bicarbonate comprises NH 4 HCO 3 And NaHCO 3 At least one of;
preferably, the concentration of the first precipitator in the precipitator solution is 200-260g/L;
preferably, the phosphate comprises NH 4 H 2 PO 4 、(NH 4 ) 2 HPO 4 And (NH) 4 ) 3 PO 4 At least one of;
preferably, the concentration of phosphate in the precipitant solution is 2-5g/L.
6. The method according to any one of claims 3 to 5, wherein the ratio of the flow rates of the metal solution and the precipitant solution is 1 (1-2);
the base solution is a mixed solution of carbonate and phosphate, or the base solution is water;
preferably, the concentration of the carbonate in the base solution is 0-50g/L, and the concentration of the phosphate in the base solution is 0-1g/L.
7. The method according to any one of claims 3 to 6, wherein the temperature of the coprecipitation reaction is 40 to 60 ℃;
preferably, the pH of the co-precipitation reaction is 7.0-7.6.
8. Doped cobalt oxide, which is characterized in that the doped cobalt oxide is prepared by calcining the doped cobalt carbonate of claim 1 or 2;
preferably, the temperature of the calcination is 500-800 ℃.
9. A lithium cobaltate prepared using the doped cobalt oxide of claim 8.
10. A battery characterized in that the lithium cobaltate according to claim 9 is contained in a positive electrode of the battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211471456.7A CN115893512A (en) | 2022-11-23 | 2022-11-23 | Doped cobalt carbonate and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211471456.7A CN115893512A (en) | 2022-11-23 | 2022-11-23 | Doped cobalt carbonate and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115893512A true CN115893512A (en) | 2023-04-04 |
Family
ID=86472244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211471456.7A Pending CN115893512A (en) | 2022-11-23 | 2022-11-23 | Doped cobalt carbonate and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115893512A (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101150190A (en) * | 2007-10-30 | 2008-03-26 | 天津巴莫科技股份有限公司 | Anode material zirconium and phosphor adulterated lithium cobaltate of lithium ion secondary battery and its making method |
| CN103384931A (en) * | 2010-12-23 | 2013-11-06 | 野猫技术开发公司 | Lithium-ion battery materials with improved properties |
| CN103779556A (en) * | 2014-01-26 | 2014-05-07 | 中信国安盟固利电源技术有限公司 | Doped and surface coating co-modified anode material for lithium ion battery and preparation method thereof |
| CN105047906A (en) * | 2015-08-21 | 2015-11-11 | 湖南杉杉新材料有限公司 | Lithium-cobalt composite oxide cathode material and preparation method thereof |
| CN105870432A (en) * | 2016-06-28 | 2016-08-17 | 中南民族大学 | Method of adopting phosphorus fertilizer product for ultrasonic spraying to prepare multi-position collaborative doped LiFePO4/C |
| WO2016155313A1 (en) * | 2015-03-31 | 2016-10-06 | 南通瑞翔新材料有限公司 | High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method therefor |
| WO2016209626A1 (en) * | 2015-06-26 | 2016-12-29 | A123 Systems, LLC | Nanoscale pore structure cathode for high power applications and material synthesis methods |
| CN107093713A (en) * | 2017-04-07 | 2017-08-25 | 武汉大学 | A kind of anion doped sodium-ion battery oxide anode material |
| CN108123109A (en) * | 2016-11-28 | 2018-06-05 | 华为技术有限公司 | Lithium cobaltate cathode material and preparation method thereof and lithium rechargeable battery |
| CN108493435A (en) * | 2018-05-31 | 2018-09-04 | 电子科技大学 | Anode material for lithium-ion batteries Li (Ni0.8Co0.1Mn0.1)1-xYxO2And preparation method |
| CN109004198A (en) * | 2018-07-26 | 2018-12-14 | 宁德新能源科技有限公司 | Metal oxide and preparation method thereof |
| CN109786738A (en) * | 2017-11-15 | 2019-05-21 | 华为技术有限公司 | A kind of high voltage lithium cobalt oxide anode and preparation method thereof and lithium ion battery |
| CN111370686A (en) * | 2020-03-20 | 2020-07-03 | 昆明理工大学 | Anion-cation co-doped modified lithium-rich manganese composite cathode material and preparation method thereof |
-
2022
- 2022-11-23 CN CN202211471456.7A patent/CN115893512A/en active Pending
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101150190A (en) * | 2007-10-30 | 2008-03-26 | 天津巴莫科技股份有限公司 | Anode material zirconium and phosphor adulterated lithium cobaltate of lithium ion secondary battery and its making method |
| CN103384931A (en) * | 2010-12-23 | 2013-11-06 | 野猫技术开发公司 | Lithium-ion battery materials with improved properties |
| CN103779556A (en) * | 2014-01-26 | 2014-05-07 | 中信国安盟固利电源技术有限公司 | Doped and surface coating co-modified anode material for lithium ion battery and preparation method thereof |
| WO2016155313A1 (en) * | 2015-03-31 | 2016-10-06 | 南通瑞翔新材料有限公司 | High-capacity nickel-cobalt-based lithium ion positive electrode material and preparation method therefor |
| WO2016209626A1 (en) * | 2015-06-26 | 2016-12-29 | A123 Systems, LLC | Nanoscale pore structure cathode for high power applications and material synthesis methods |
| CN105047906A (en) * | 2015-08-21 | 2015-11-11 | 湖南杉杉新材料有限公司 | Lithium-cobalt composite oxide cathode material and preparation method thereof |
| CN105870432A (en) * | 2016-06-28 | 2016-08-17 | 中南民族大学 | Method of adopting phosphorus fertilizer product for ultrasonic spraying to prepare multi-position collaborative doped LiFePO4/C |
| CN108123109A (en) * | 2016-11-28 | 2018-06-05 | 华为技术有限公司 | Lithium cobaltate cathode material and preparation method thereof and lithium rechargeable battery |
| CN107093713A (en) * | 2017-04-07 | 2017-08-25 | 武汉大学 | A kind of anion doped sodium-ion battery oxide anode material |
| CN109786738A (en) * | 2017-11-15 | 2019-05-21 | 华为技术有限公司 | A kind of high voltage lithium cobalt oxide anode and preparation method thereof and lithium ion battery |
| CN108493435A (en) * | 2018-05-31 | 2018-09-04 | 电子科技大学 | Anode material for lithium-ion batteries Li (Ni0.8Co0.1Mn0.1)1-xYxO2And preparation method |
| CN109004198A (en) * | 2018-07-26 | 2018-12-14 | 宁德新能源科技有限公司 | Metal oxide and preparation method thereof |
| CN111370686A (en) * | 2020-03-20 | 2020-07-03 | 昆明理工大学 | Anion-cation co-doped modified lithium-rich manganese composite cathode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘国聪;刘又年;刘素琴;董辉;: "锂离子电池正极材料Li_3V_(2-2x/3)Mn_x(PO_4)_3的溶胶凝胶法合成和电化学性能", 无机材料学报, no. 10 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111916727B (en) | Dual-ion wet-doped ternary high-nickel cathode material and preparation method thereof | |
| CN108963228B (en) | Method for preparing ternary positive electrode material of lithium ion battery on metal organic framework material ZIF-8 and product | |
| EP2763219A2 (en) | Precursor of a cathode active material for a lithium secondary battery, cathode active material, method for manufacturing the cathode active material, and lithium secondary battery including the cathode active material | |
| CN111653752B (en) | Cathode material, preparation method thereof and lithium ion battery | |
| CN110890535A (en) | Cathode material, preparation method thereof and application of cathode material in lithium ion battery | |
| CN110492097B (en) | NCM ternary composite positive electrode material and preparation and application thereof | |
| KR101744091B1 (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| CN112531158B (en) | High-nickel ternary single crystal material and preparation method thereof | |
| CN109755512A (en) | A kind of nickelic long-life multielement positive electrode and preparation method thereof | |
| KR20070103023A (en) | Method for producing lithium containing complex oxide for positive electrode of lithium secondary battery | |
| CN106910887A (en) | A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode | |
| JP2007299668A (en) | Positive electrode active material for nonaqueous electrolyte battery, and nonaqueous electrolyte battery using it | |
| CN112421010A (en) | Cathode material, preparation method thereof and lithium ion battery | |
| WO2023109194A1 (en) | Positive electrode material with high peak-intensity ratio, and preparation method therefor and use thereof | |
| KR20150144613A (en) | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same | |
| KR20240011822A (en) | Surface coated cathode material and manufacturing method thereof, lithium ion battery | |
| CN113782735A (en) | Sodium ion battery positive electrode material, sodium ion battery, preparation method and electric equipment | |
| CN115064670A (en) | Preparation method of doped coated modified sodium nickel manganese oxide cathode material | |
| CN115810757B (en) | Positive electrode active material and lithium ion battery containing same | |
| CN109216692B (en) | Modified ternary cathode material, preparation method thereof and lithium ion battery | |
| CN108807971B (en) | Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof | |
| CN111233052A (en) | Nickel cobalt lithium manganate ternary positive electrode material, preparation method thereof, positive electrode and battery | |
| CN116805684A (en) | Al, zn, ti and Fe co-doped biphase layered oxide sodium ion battery high-entropy positive electrode material | |
| CN116979039A (en) | Perovskite type conductor coated ternary positive electrode material and preparation method thereof | |
| CN115911331A (en) | Preparation method of low-nickel copper manganese-based sodium ion battery positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |